Process for producing polar olefin copolymer and polar olefin copolymer obtained thereby

ABSTRACT

A process for producing a polar olefin copolymer comprises copolymerizing a non-polar olefin and a polar olefin in the presence of a transition metal compound selected from Groups 4, 5, 6 and 11 of the periodic table, which is represented by the following formula (IV):  
                 
 
     wherein M′ is a transition metal atom selected from Groups 4, 5, 6 and 11 of the periodic table, m is an integer of 1 to 6, A is —O—, —Si—, —Se—, —N(R 6 )—, n is a number satisfying a valence of M′, R 1  to R 4  and R 6  are each a hydrogen atom, a halogen atom, a hydrocarbon group and the like, and X is a halogen atom, an oxygen atom, a hydrocarbon group and the like, and at least one compound (B) selected from the group consisting of an organometallic compound (B-1), an organoaluminum oxy-compound (B-2) and an ionic ionizing compound (B-3). Therefore, the process is capable of obtaining a polar olefin copolymer having excellent properties under mild polymerization conditions.

FIELD OF THE INVENTION

[0001] The present invention relates to a process for producing a polarolefin copolymer and a polar olefin copolymer obtained by the process.More particularly relates to a process for producing a polar olefincopolymer comprising copolymerizing a non-polar olefin and a polarolefin in the presence of a specific catalyst and a polar olefincopolymer obtained by the process.

BACKGROUND OF THE INVENTION

[0002] The olefin polymer is generally excellent in mechanicalproperties, and hence has widely been employed in varied fields such asones of molded products of all sorts. However, since the demands forphysical properties of olefin polymers have been diversified recently,olefin polymers with various properties have increasingly been desired.

[0003] As an example of olefin polymers satisfying such demands, knownis a polar olefin copolymer obtained by copolymerizing a non-polarolefin and a polar olefin to provide properties which cannot be expectedin a polymer consisting of non-polar olefins only. Radicalpolymerization method is well known as a conventional process forproducing a polar olefin copolymer by copolymerizing a non-polar olefinand a polar olefin, and for example, ethylene-vinyl acetate copolymersand ethylene-acrylic ester copolymers have been produced by this method.

[0004] In producing a polar olefin copolymer by the radicalpolymerization method, reaction conditions at a high temperature andunder high pressure are often required. In view of such circumstances,there has been desired a process capable of producing a polar olefincopolymer under more moderate conditions.

[0005] As a process for producing a polar olefin copolymer under lessstrict conditions than the conventional ones, the process forcopolymerizing a non-polar olefin and a polar olefin using a transitionmetal complex catalyst has been reported recently. For example,Brookhart et al. disclosed a process for producing a copolymer of anon-polar olefin such as ethylene and methyl acrylate under moderateconditions using a diimine complex of palladium (J. Am. Chem. Soc. 1998,120, 888 etc.). There are only a few cases, however, in which anon-polar olefin and a polar olefin have been copolymerized by using atransition metal complex catalyst, and the kinds of polar olefinsemployable to be copolymerized are still limited.

[0006] In the above situation, there has been desired the development ofa process for producing a polar olefin copolymer which is superior inthe capacity for copolymerizing a polar olefin and capable of obtaininga polar olefin copolymer with excellent properties.

OBJECT OF THE INVENTION

[0007] The present invention has been made in light of the abovesituation of the prior art. An object of the present invention is toprovide a process for producing a polar olefin copolymer capable ofobtaining a polar olefin copolymer with excellent properties under mildpolymerization conditions, and also to provide a polar olefin copolymerobtained by the process.

SUMMARY OF THE INVENTION

[0008] The process for preparing a polar olefin copolymer of the presentinvention comprises:

[0009] copolymerizing a non-polar olefin and a polar olefin in thepresence of a catalyst comprising

[0010] (A0) a compound of a transition metal selected from Groups 3 to11 of the periodic table, which is represented by the following formula(1):

L_(m)MX_(n)  (1)

[0011] wherein M is a transition metal atom selected from Groups 3 to 11of the periodic table,

[0012] m is an integer of 1 to 6,

[0013] n is a number satisfying a valence of M,

[0014] L is a ligand coordinated to M and each ligand L has a featurethat when the value obtained by subtracting the total sum of the wholeenergy, as determined by a density functional method, of the compoundson the left-hand member from the whole energy, as determined by adensity functional method, of the compound on the right-hand member inthe following chemical formula (2) and the value obtained by the samesubtraction in the following chemical formula (3) are defined ascoordination energy E₁ of ethylene and coordination energy E₂ of methylacrylate, respectively, the difference ΔE (ΔE=E₁-E₂) between thecoordination energy E₁ of ethylene and the coordination energy E₂ ofmethyl acrylate is 50 kJ/mol or less,

[0015] wherein M is the same transition metal atom selected from Groups3 to 11 of the periodic table as M in the formula (1), a is an integerof 1 to 3, b is an electric charge of the compound in the blankets [ ]and is 0 or +1, and Me is a methyl group, and

[0016] X is a hydrogen atom, a halogen atom, an oxygen atom, ahydrocarbon group, an oxygen-containing group, a sulfur-containinggroup, a nitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residual group,silicon-containing group, a germanium-containing group and atin-containing group, and when n is 2 or greater, plural atoms or groupsindicated by X may be the same or different, and plural groups indicatedby X may be bonded to each other to form a ring.

[0017] The other embodiment of the process for preparing a polar olefincopolymer of the invention comprises:

[0018] copolymerizing a non-polar olefin and a polar olefin in thepresence of a catalyst comprising

[0019] (A0) a compound of a transition metal selected from Groups 3 to11 of the periodic table, which is represented by the above formula (1),and

[0020] (B) at least one compound selected from the group consisting of

[0021] (B-1) an organometallic compound,

[0022] (B-2) an organoaluminum oxy-compound, and

[0023] (B-3) a compound which reacts with a transition metal compound(A0) to form an ion pair.

[0024] In the present invention, the transition metal compound of theformula (1) is preferably a compound of a transition metal selected fromGroups 4, 5, 6 and 11 of the periodic table.

[0025] Further, the other embodiment of the process for producing apolar olefin copolymer of the invention comprises:

[0026] copolymerizing a non-polar olefin and a polar olefin in thepresence of a catalyst comprising:

[0027] (A1) a reaction product of

[0028] (C) a compound of a transition metal selected from Groups 4, 5, 6and 11 of the periodic table which is represented by the followingformula (c):

M′X_(k)  (c)

[0029] wherein M′ is a transition metal atom selected from Groups 4, 5,6 and 11 of the periodic table,

[0030] k is a number satisfying a valence of M′, and

[0031] X is a hydrogen atom, a halogen atom, an oxygen atom, ahydrocarbon group, an oxygen-containing group, a sulfur-containinggroup, a nitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residual group, asilicon-containing group, a germanium-containing group or atin-containing group, and when k is 2 or greater, plural atoms or groupsindicated by X may be the same or different, and plural groups indicatedby X may be bonded to each other to form a ring, and

[0032] (A-i) a compound represented by the following formula (I):

[0033] wherein A is an oxygen atom, a sulfur atom or a selenium atom, ora nitrogen atom having a substituent R⁶, and

[0034] R¹ to R⁶ may be the same or different, they are each a hydrogenatom, a halogen atom, a hydrocarbon group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group, a boron-containinggroup, an aluminum-containing group, a phosphorus-containing group, aheterocyclic compound residual group, a silicon-containing group, agermanium-containing group or a tin-containing group, two or more ofthem may be bonded to each other to form a ring; and

[0035] (B) at least one compound selected from the group consisting of:

[0036] (B-1) an organometallic compound,

[0037] (B-2) an organoaluminum oxy-compound, and

[0038] (B-3) a compound which reacts with the reaction product (A1) toform an ion pair.

[0039] Further, the other embodiment of the process for producing apolar olefin of the invention comprises:

[0040] copolymerizing a non-polar olefin and a polar olefin in thepresence of a catalyst comprising:

[0041] (A2) a reaction product of

[0042] (C) a compound of a transition metal selected from Groups 4, 5, 6and 11 of the periodic table, which is represented by the above formula(c), and

[0043] (A-ii) a compound represented by the following formula (II):

[0044] wherein D is a nitrogen atom or a phosphorus atom,

[0045] Q is a nitrogen atom or a phosphorus atom, or a carbon atomsubstituted with a substituent R¹³,

[0046] S is a nitrogen atom or a phosphorus atom, or a carbon atomsubstituted with a substituent R¹⁴,

[0047] T is a nitrogen atom or a phosphorus atom, or a carbon atomsubstituted with a substituent R¹⁵,

[0048] R¹¹ to R¹⁶ may be the same or different, they are each a hydrogenatom, a halogen atom, a hydrocarbon group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group, a boron-containinggroup, an aluminum-containing group, a phosphorus-containing group, aheterocyclic compound residual group, a silicon-containing group, agermanium-containing group or a tin-containing group, two or more ofthem may be bonded to each other to form a ring; and

[0049] (B) at least one compound selected from the group consisting of:

[0050] (B-1) an organometallic compound,

[0051] (B-2) an organoaluminum oxy-compound, and

[0052] (B-3) a compound which reacts with the reaction product (A2) toform an ion pair.

[0053] Further, the other embodiment of the process for producing apolar olefin copolymer of the invention comprises:

[0054] copolymerizing a non-polar olefin and a polar olefin in thepresence of a catalyst comprising:

[0055] (A3) a reaction product of

[0056] (C′) a compound of a transition metal selected from Groups 3 to11 of the periodic table, which is represented by the following formula(c′):

MX_(k)  (c′)

[0057] wherein M is a transition metal atom selected from Groups 3 to 11of the periodic table,

[0058] k is a number satisfying a valence of M, and

[0059] X is a hydrogen atom, a halogen atom, an oxygen atom, ahydrocarbon group, an oxygen-containing group, a sulfur-containinggroup, a nitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residual group, asilicon-containing group, a germanium-containing group or atin-containing group, and when k is 2 or greater, plural atoms or groupsindicated by X may be the same or different, and plural groups indicatedby X may be bonded to each other to form a ring, and

[0060] (A-iii) a compound represented by the following formula (III):

[0061] wherein A is an oxygen atom, a sulfur atom or a selenium atom, ora nitrogen atom having a substituent R²⁶, and

[0062] R²¹ to R²⁸ may be the same or different, they are each a hydrogenatom, a halogen atom, a hydrocarbon group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group, a boron-containinggroup, an aluminum-containing group, a phosphorus-containing group, aheterocyclic compound residual group, a silicon-containing group, agermanium-containing group or a tin-containing group, two or more ofthem may be bonded to each other to form a ring.

[0063] The other embodiment of the process for producing a polar olefincopolymer of the invention comprises:

[0064] copolymerizing a non-polar olefin and a polar olefin in thepresence of a catalyst comprising:

[0065] (A3) a reaction product of

[0066] (C′) a compound of a transition metal selected from Groups 3 to11 of the periodic table, which is represented by the above formula(c′), and

[0067] (A-iii) a compound represented by the above formula (III); and

[0068] (B) at least one compound selected from the group consisting of:

[0069] (B-1) an organometallic compound,

[0070] (B-2) an organoaluminum oxy-compound, and

[0071] (B-3) a compound which reacts with the transition metal compound(A3) to form an ion pair.

[0072] In the present invention, the transition metal compound of theformula (c′) is preferably a compound of a transition metal selectedfrom Groups 4, 5, 6 and 11 of the periodic table.

[0073] Further, the other embodiment of the process for producing apolar olefin copolymer of the invention comprises:

[0074] copolymerizing a non-polar olefin and a polar olefin in thepresence of a catalyst comprising:

[0075] (A4) a compound of a transition metal selected from Groups 4, 5,6 and 11 of the periodic table, which is represented by the followingformula (IV):

[0076] wherein M′ has the same meaning as that of M′ in the formula (c),

[0077] m is an integer of 1 to 6,

[0078] A, R¹ to R⁴ and R⁶ have the same meanings as those of A, R¹ to R⁴and R⁶ in the formula (I),

[0079] n is a number satisfying a valence of M′, and

[0080] X has the same meaning as that of X in the formula (1), and whenn is 2 or greater, plural atoms or groups indicated by X may be the sameor different, and plural groups indicated by X may be bonded to eachother to form a ring, and

[0081] (B) at least one compound selected from the group consisting of:

[0082] (B-1) an organometallic compound,

[0083] (B-2) an organoaluminum oxy-compound, and

[0084] (B-3) a compound which reacts with the transition metal compound(A4) to form an ion pair.

[0085] Further, the other embodiment of the process for producing apolar olefin copolymer of the invention comprises:

[0086] copolymerizing a non-polar olefin and a polar olefin in thepresence of a catalyst comprising:

[0087] (A5) a compound of a transition metal selected from Groups 4, 5,6 and 11 of the periodic table which is represented by the followingformula (V)

[0088] wherein M′ has the same meaning as that of M′ in the formula (c),

[0089] m is an integer of 1 to 6,

[0090] D, Q, S, T and R¹¹ to R¹⁵ have the same meanings as those of D,Q, S, T and R¹¹ to R¹⁵ in the formula (II),

[0091] n is a number satisfying a valence of M′, and

[0092] X has the same meaning as that of X in the formula (1), and whenn is 2 or greater, plural atoms or groups indicated by X may be the sameor different, and plural groups indicated by X may be bonded to eachother to form a ring, and

[0093] (B) at least one compound selected from the group consisting of:

[0094] (B-1) an organometallic compound,

[0095] (B-2) an organoaluminum oxy-compound, and

[0096] (B-3) a compound which reacts with the transition metal compound(A5) to form an ion pair.

[0097] Further, the other embodiment of the process for producing apolar olefin copolymer of the invention comprises:

[0098] copolymerizing a non-polar olefin and a polar olefin in thepresence of a catalyst comprising:

[0099] (A6) a compound of a transition metal selected from Groups 3 to11 of the periodic table, which is represented by the following formula(VI):

[0100] wherein M has the same meaning as that of M in the formula (C′),

[0101] m is an integer of 1 to 6,

[0102] A and R²¹ to R²⁷ have the same meanings as those of A and R²¹ toR²⁷ in the formula (III),

[0103] n is a number satisfying a valence of M, and

[0104] X has the same meaning as that of X in the formula (1), and whenn is 2 or greater, plural atoms or groups indicated by X may be the sameor different, and plural groups indicated by X may be bonded to eachother to form a ring.

[0105] The other embodiment of the process for producing a polar olefincopolymer of the present invention comprises copolymerizing a non-polarolefin and a polar olefin in the presence of a catalyst comprising:

[0106] (A6) a compound of a transition metal selected from Groups 3 to11 of the periodic table, which is represented by the above formula(VI), and

[0107] (B) at least one compound selected from the group consisting of:

[0108] (B-1) an organometallic compound,

[0109] (B-2) an organoaluminum oxy-compound, and

[0110] (B-3) a compound which reacts with the transition metal compound(A6) to form an ion pair.

[0111] In the present invention, the transition metal compound of theformula (VI) is preferably a compound of a transition metal selectedfrom Groups 4, 5, 6 and 11 of the periodic table.

[0112] The polar olefin copolymer of the present invention is obtainedby any of the above processes.

[0113] Hereinafter, a compound which reacts with a reaction product (A1)to form an ion pair, a compound which reacts with a reaction product(A2) to form an ion pair, a compound which reacts with a reactionproduct (A3) to form an ion pair, a compound which reacts with atransition metal compound (A4) to form an ion pair, a compound whichreacts with a transition metal compound (A5) to form an ion pair and acompound which reacts with a transition metal compound (A6) to form anion pair are referred to as “ionizing ionic compound”.

BRIEF DESCRIPTION OF THE DRAWING

[0114]FIG. 1 is an explanatory diagram, which illustrates one embodimentof the preparation process of an olefin polymerization catalyst to beused in the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0115] The process for preparing a polar olefin copolymer according tothe present invention is described in detail hereinafter.

[0116] The process for preparing a polar olefin copolymer according tothe invention comprises:

[0117] copolymerizing a non-polar olefin and a polar olefin in thepresence of a catalyst comprising

[0118] a compound (A0) of a transition metal selected from Groups 3 to11 of the periodic table, which is represented by the formula (1)wherein each ligand L has a feature that when the value obtained bysubtracting the total sum of the whole energy, as determined by adensity functional method, of the compounds on the left-hand member fromthe whole energy, as determined by a density functional method, of thecompound on the right-hand member in the chemical formula (2) and thevalue obtained by the same subtraction in the chemical formula (3) aredefined as coordination energy E₁ of ethylene and coordination energy E₂of methyl acrylate, respectively, the difference ΔE (ΔE=E₁-E₂) betweenthe coordination energy E₁ of ethylene and the coordination energy E₂ ofmethyl acrylate is not more than 50 kJ/mol, and optionally,

[0119] at least one compound (B) selected from the group consisting ofan organometallic compound (B-1), an organoaluminum oxy-compound (B-2)and an ionizing ionic compound (B-3); or

[0120] copolymerizing a non-polar olefin and a polar olefin in thepresence of a catalyst comprising

[0121] a reaction product of a compound (C) of a transition metalselected from Groups 4, 5, 6 and 11 of the periodic table, said compound(C) being represented by the following formula (c), and a compoundrepresented by the following formula (I) or (II), and

[0122] at least one compound (B) selected from the group consisting ofan organometallic compound (B-1), an organoaluminum oxy-compound (B-2)and an ionizing ionic compound (B-3); or

[0123] copolymerizing a non-polar olefin and a polar olefin in thepresence of a catalyst comprising

[0124] a reaction product of a compound (C′) of a transition metalselected from Groups 3 to 11 of the periodic table, said compound (C′)being represented by the following formula (c′), and a compoundrepresented by the following formula (III), and optionally,

[0125] at least one compound (B) selected from the group consisting ofan organometallic compound (B-1), an organoaluminum oxy-compound (B-2)and an ionizing ionic compound (B-3); or

[0126] copolymerizing a non-polar olefin and a polar olefin in thepresence of a catalyst comprising

[0127] a compound of a transition metal selected from Groups 4, 5, 6 and11 of the periodic table, said compound being represented by thefollowing formula (IV) or (V), and

[0128] at least one compound (B) selected from the group consisting ofan organometallic compound (B-1), an organoaluminum oxy-compound (B-2)and an ionizing ionic compound (B-3); or

[0129] copolymerizing a non-polar olefin and a polar olefin in thepresence of a catalyst comprising a compound of a transition metalselected from Groups 3 to 11 of the periodic table, said compound beingrepresented by the following formula (VI), and optionally,

[0130] at least one compound (B) selected from the group consisting ofan organometallic compound (B-l), an organoaluminum oxy-compound (B-2)and an ionizing ionic compound (B-3).

[0131] At first, the components forming the catalyst employed in thepresent invention are described below in order.

[0132] Transition Metal Compound (A0)

[0133] The transition metal compound (AO) is represented by thefollowing formula (1)

L_(m)MX_(n)  (1)

[0134] In the formula (1), M is a transition metal atom selected fromGroups 3 to 11, preferably Groups 4, 5, 6 and 11, of the periodic table.Specific examples of such transition metal atoms include scandium,yttrium, lanthanoid, titanium, zirconium, hafnium, vanadium, niobium,tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron,ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper andsilver. Of these, preferable are transition metal atoms selected fromGroups 4, 5, 6 and 11 of the periodic table, such as titanium,zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum,tungsten, copper and silver, and more preferable are titanium, vanadiumand chromium.

[0135] In the formula (1), m is an integer of 1 to 6, preferably aninteger of 1 to 4.

[0136] In the formula (1), n is a number satisfying a valence of M,specifically an integer of 0 to 5, preferably an integer of 1 to 4, morepreferably an integer of 1 to 3.

[0137] In the formula (1), L is a ligand coordinated to M and eachligand L has a feature that when the value obtained by subtracting thetotal sum of the whole energy, as determined by a density functionalmethod, of the compounds on the left-hand member from the whole energy,as determined by a density functional method, of the compound on theright-hand member in the chemical formula (2) and the value obtained bythe same subtraction in the chemical formula (3) are defined ascoordination energy El of ethylene and coordination energy E₂ of methylacrylate, respectively, the difference ΔE (ΔE=E₁-E₂) between thecoordination energy E₁ of ethylene and the coordination energy E₂ ofmethyl acrylate is not more than 50 kJ/mol.

[0138] In the chemical formulas (2) and (3), M is the same transitionmetal atom selected from Groups 3 to 11 of the periodic table as M inthe formula (1).

[0139] This ligand L may take any coordination form to the metal so longas the coordination energy difference ΔE is not more than 50 kJ/mol.Examples of the coordination forms include covalent bond, coordinatebond, ionic bond and hydrogen bond. Further, the ligand L may be amonodentate ligand or a polydentate ligand such as a bidentate ligandcoordinated to the transition metal atom M, and to the metal, any atomof the ligand L may be coordinated.

[0140] In the chemical formulas (2) and (3), a is a number of theligands L, and b is an electric charge of the compound in the brackets []. b is 0 or +1. a is determined by the ligand L and a valence of thetransition metal atom M, and is selected from integers of 1 to 3 so thatthe electric charge of the compound [L_(a)—M—Me] can be 0 or +1.

[0141] In the chemical formulas (2) and (3), Me is a methyl group.

[0142] In the process of the invention, the value obtained bysubtracting the total sum of the whole energy, as determined by adensity functional method, of the compounds on the left-hand member fromthe whole energy, as determined by a density functional method, of thecompound on the right-hand member in the chemical formula (2) and thevalue obtained by the same subtraction in the chemical formula (3) aredefined as coordination energy E₁ of ethylene and coordination energy E₂of methyl acrylate, respectively.

[0143] The density functional method used herein means calculation usingProgram ADF2000.01 and using BLYP method.

[0144] In the calculation procedure, the structure of each compound inthe chemical formulas (2) and (3) is optimized, and the whole energy ofeach compound having the optimized structure is calculated. Then, thetotal sum of the whole energy of the compounds on the left-hand memberin the chemical formula (2) is subtracted from the whole energy of thecompound on the right-hand member in the chemical formula (2), and thevalue obtained is taken as coordination energy E₁ of ethylene. Likewise,the total sum of the whole energy of the compounds on the left-handmember in the chemical formula (3) is subtracted from the whole energyof the compound on the right-hand member in the chemical formula (3),and the value obtained is taken as coordination energy E₂ of methylacrylate.

[0145] In the optimization of the structure, for the central metal, atriple zeta type function is used as a basis function, for atoms bondedto the metal atom among a methyl group coordinated to the central metal,all atoms in ethylene and methyl acrylate and atoms in the ligand L,double zeta type functions are used as basis functions, and for theother atoms, single zeta type functions are used as basis functions. Inthe chemical formula (3), a structure in which oxygen of the carbonylgroup is coordinated to the central metal M of the complex is shown as acoordination structure of methyl acrylate, and the coordinationstructure is determined by the result of the structure optimizationcalculation. As a result of the calculation, if the olefinic carbon ofmethyl acrylate and the central metal M have mutual interaction, thewhole energy of the compound is calculated using the structure.

[0146] Then, the whole energy of the thus obtained optimum structure iscalculated. In this case, for the central metal, a triple zeta typefunction is used as a basis function, and for the other atoms, functionsobtained by adding polarization functions to double zeta type functionsare used as basis functions. In addition, correction of Pauli'srelativistic potential is made. Based on the whole energy of eachcompound, the total sum of the whole energy of the compounds on theleft-hand member is subtracted from the whole energy of the compound onthe right-hand member in each of the chemical formulas (2) and (3), andthe values obtained on the chemical formulas (2) and (3) are taken ascoordination energy E₁ of ethylene and coordination energy E₂ of methylacrylate, respectively. Then, the difference ΔE between the coordinationenergy E₁ of ethylene and the coordination energy E₂ of methyl acrylateis calculated according to the equation ΔE=E₁-E₂.

[0147] In the present invention, a non-polar olefin and a polar olefinare copolymerized in the presence of a catalyst comprising a compound ofa transition metal selected from Groups 3 to 11 of the periodic table,said compound containing each ligand L having a difference ΔE, betweenthe coordination energy of ethylene and the coordination energy ofmethyl acrylate, of not more than 50 kJ/mol and being represented by theabove formula (1).

[0148] Each of the coordination energy E₁ of ethylene and thecoordination energy E₂ of methyl acrylate indicates a degree ofstabilization due to coordination of each monomer to the transitionmetal, and the difference ΔE is a measure of difference between thedegrees of stabilization. In the present invention, the difference ΔE isnot more than 50 kJ/mol, preferably not more than 30 kJ/mol, morepreferably not more than 20 kJ/mol.

[0149] In the formula (1), X denotes a hydrogen atom, a halogen atom, anoxygen atom, a hydrocarbon group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group, a boron-containinggroup, an aluminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residual group, asilicon-containing group, a germanium-containing group or atin-containing group. When X is an oxygen atom, M and X are bondedthrough a double bond.

[0150] Examples of the halogen atoms include fluorine, chlorine, bromineand iodine.

[0151] Examples of the hydrocarbon groups include alkyl groups such asmethyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl and eicosyl;cycloalkyl groups of 3 to 30 carbon atoms such as cyclopentyl,cyclohexyl, norbornyl and adamantyl; alkenyl groups such as vinyl,propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyland phenylpropyl; and aryl groups such as phenyl, tolyl, dimethylphenyl,trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl,methylnaphthyl, anthryl and phenanthryl. These hydrocarbon groups mayalso include halogenated hydrocarbon groups, specifically those groupsof 1 to 30 carbon atoms in which at least one hydrogen is replaced withhalogen. Of these, hydrocarbon groups of 1 to 20 carbon atoms arepreferable.

[0152] Examples of the oxygen-containing groups include an oxy group; aperoxy group; a hydroxy group; a hydroperoxy group; alkoxy groups suchas methoxy, ethoxy, propoxy and butoxy; aryloxy groups such as phenoxy,methylphenoxy, dimethylphenoxy and naphthoxy; arylalkoxy groups such asphenylmethoxy and phenylethoxy; an acetoxy group; a carbonyl group; anacetylacetonato group (acac); and an oxo group.

[0153] Examples of the sulfur-containing groups include sulfonato groupssuch as methylsulfonato, trifluoromethanesulfonato, phenylsulfonato,benzylsulfonato, p-toluenesulfonato, trimethylbenzenesulfonato,triisobutylbenzenesulfonato, p-chlorobenzenesulfonato andpentafluorobenzenesulfonato; sulfinato groups such as methylsulfinato,phenylsulfinato, benzylsulfinato, p-toluenesulfinato,trimethylbenzenesulfinato and pentafluorobenzenesulfinato; an alkylthiogroup; an arylthio group; a sulfate group; a sulfide group; apolysulfide group; and a thiolate group.

[0154] Examples of the nitrogen-containing groups include an aminogroup; alkylamino groups such as methylamino, dimethylamino,diethylamino, dipropylamino, dibutylamino and dicyclohexylamino;arylamino or alkylarylamino groups such as phenylamino, diphenylamino,ditolylamino, dinaphthylamino and methylphenylamino; and alkyl orarylamine groups such as trimethyamine, triethylamine, triphenylamine,N,N,N′,N′-tetramethylethylenediamine (tmeda) andN,N,N′,N′-tetraphenylpropylenediamine (tppda).

[0155] Examples of the boron-containing groups include BR₄(R ishydrogen, an alkyl group, an aryl group which may have a substituent, ahalogen atom or the like).

[0156] Examples of the aluminum-containing groups include AlR₄ (R ishydrogen, an alkyl group, an aryl group which may have a substituent, ahalogen atom or the like).

[0157] Examples of the phosphorus-containing groups includetrialkylphosphine groups such as trimethylphosphine, tributylphosphineand tricyclohexylphosphine; triarylphosphine groups such astriphenylphosphine and tritolylphosphine; phosphite groups (phosphidogroups) such as methylphosphite, ethylphosphite and phenylphosphite; aphosphonic acid group; and a phosphinic acid group.

[0158] Examples of the halogen-containing groups includefluorine-containing groups such as PF₆ and BF₄; chlorine-containinggroups such as ClO₄ and SbCl₆; and iodine-containing groups such as IO₄.

[0159] Examples of the heterocyclic compound residual groups includeresidual groups of nitrogen-containing compounds such as pyrrole,pyridine, pyrimidine, quinoline and triazine, oxygen-containingcompounds such as furan and pyran and sulfur-containing compounds suchas thiophene; and these heterocyclic compound residual groups which arefurther substituted with substituents such as alkyl or alkoxy groups of1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

[0160] Examples of the silicon-containing groups includehydrocarbon-substituted silyl groups such as phenylsilyl, diphenylsilyl,trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl,triphenylsilyl, methyldiphenylsilyl, tritolylsilyl and trinaphthylsilyl;hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether;silicon-substituted alkyl groups such as trimethylsilylmethyl; andsilicon-substituted aryl groups such as trimethylsilylphenyl.

[0161] Examples of the germanium-containing groups include groupswherein silicon is replaced with germanium in the aforesaidsilicon-containing groups.

[0162] Examples of the tin-containing groups include groups whereinsilicon is replaced with tin in the aforesaid silicon-containing groups.

[0163] When k is 2 or greater, plural atoms or groups indicated by X maybe the same or different, and plural groups indicated by X may be bondedto each other to form a ring.

[0164] The bond form between X and the transition metal atom M is notspecifically restricted, and examples of the bond forms between X andthe transition metal atom M include covalent bond, coordinate bond,ionic bond and hydrogen bond.

[0165] The ligands L and the transition metal atoms M in the formula (1)is quite the same as those in the chemical formulas (2) and (3),including the valence of the metal, but the numbers a of the ligands andn in those formulas are not necessarily equal to each other.

[0166] Reaction Product (A1)

[0167] The reaction product (A1) is a reaction product of a compound (C)of a transition metal selected from Groups 4, 5, 6 and 11 of theperiodic table which is represented by the following formula (c), and acompound represented by the following formula (I).

[0168] (Transition Metal Compound (C))

M′X_(k)  (c)

[0169] In the above formula (c), M′ is a transition metal atom selectedfrom Groups 4, 5, 6 and 11 of the periodic table, and examples thereofinclude metal atoms of Group 4 such as titanium, zirconium-and hafnium;metal atoms of Group 5 such as vanadium, niobium and tantalum; metalatoms of Group 6 such as chromium, molybdenum and tungsten; and metalatoms of Group 11 such as copper, silver and gold. Of these, titanium,vanadium and chromium are preferable.

[0170] X has the same meanings as that of X in the formula (1). When kis 2 or greater, plural groups indicated by X may be the same ordifferent, and plural groups indicated by X may be bonded to each otherto form a ring.

[0171] Bonding style between X and a transition metal atom M′ has nospecific restriction, and may be a covalent bond, a coordinate bond, anionic bond, a hydrogen bond or the like.

[0172] The k is a number satisfying a valence of M′, and determinedaccording to a valence of the transition metal M′ and a valence of X sothat these positive and negative valences are neutralized.

[0173] In this regard, if an absolute value of a valence of thetransition metal M′ is indicated by a, and an absolute value of avalence of X is indicated by b, then the relationship is represented bythe following formula:

a=b×k.

[0174] In particular, when M′ is Ti³⁺ and X is Cl³¹ , for example, k is3 so that the transition metal compound represented by the formula (c)becomes TiCl₃. In another case where M′ is Zr⁴⁺ and X is SO₄ ²⁻, k is 2so that the transition metal compound represented by the formula (c)becomes Zr(SO₄)₂.

[0175] Similarly, in the case where X comprises two or more groups, k isdetermined by dividing into two or more numbers in order that thepositive and negative valences are neutralized. For example, in the casewhere X comprises two kinds of groups, if an absolute value of a valenceof one of Xs is indicated by b₁, and the number thereof is indicated byk₁; and an absolute value of a valence of the other of Xs is indicatedby b₂, and the number thereof is indicated by k₂, then the relationshipis represented by the following formula:

a=b ₁ ×k ₁ +b ₂ ×k ₂.

[0176] In particular, when M′ is V⁵⁺ and Xs are O²⁻ and Cl⁻, forexample, the transition metal compound represented by the formula (c)becomes VOCl₃ or VO₂Cl. In another case where M′ is V⁴⁺ and Xs are O²⁻and SO₄ ²⁻, the transition metal compound represented by the formula (c)becomes [VO] [SO₄].

[0177] Examples of the transition metal compounds represented by theformula (c) include halides of transition metals such as TiCl₃, TiCl₄,TiBr₃, TiBr₄, ZrCl₄, ZrBr₄, HfBr₄, HfCl₄, VCl₄, VCl₅, VBr₄, VBr₅, NbCl₅,NbBr₅, TaCl₅, TaBr₄, CrCl₃, CrCl₂, MoCl₅, MoCl₃, WCl₆, WCl₅, CuCl₂,CuBr₂, AgCl₂ and AuCl₂; complex compounds of transition metal halides(e.g., TiCl₄.2(THF) and ZrCl₄.2(Et₂O)) and electron donor compounds(e.g., tetrahydrofuran (THF), acetonitrile or diethyl ether); transitionmetal compounds having halogen atoms such as oxyhalides of transitionmetals, such as ZrOCl₂, HfOCl₂, VOCl₂, VOBr, VOCl₃, NbOBr₃, CrO₂Cl₂,MoOBr, MoOCl₃, MoO₂Cl₂, WOCl₄, WO₂Br₂, CuCl₂.2CuO.4H₂O, CuBr₂.Cu(OH)₂,CuBr₂.3Cu(OH)₂; transition metal compounds having hydrocarbon groupssuch as Ti(CH₂Ph)₄; transition metal compounds having oxygen-containinggroups such as Ti(O—iPr)₄, Zr(O—iPr)₄, Cu(acac)₂, MoO(acac)₂, W(OPh)₅,Cr(acac)₃, VO(acac)₂, V(acac)₃, Mo(CO)₆, W(CO)₆ and [VO] [S₄].5H₂O; andtransition metal compounds having nitrogen-containing groups such asTi(N(Me)₂)₄ and Zr(N(Me)₂)₄.

[0178] As the transition metal compound (C), M′ is preferably titanium,vanadium, chromium or copper, and X is preferably a halogen atom, analkyl group, an oxygen-containing group or a nitrogen-containing group,more preferably a chlorine atom, a bromine atom or a methyl group.

[0179] The reaction product (A1) is a reaction product of the transitionmetal compound (C) represented by the formula (c) and the compound (A-i)represented by the following formula (I).

[0180] (Compound (A-i))

[0181] In the formula (I), A is an oxygen atom (—O—), a sulfur atom(—S—), a selenium atom (—Se—) or a nitrogen atom having a substituent R⁶(—N(R⁶)—).

[0182] R¹ to R⁶ may be the same or different, they are each a hydrogenatom, a halogen atom, a hydrocarbon group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group, a boron-containinggroup, an aluminum-containing group, a phosphorus-containing group, aheterocyclic compound residual group, a silicon-containing group, agermanium-containing group or a tin-containing group.

[0183] The halogen atoms include fluorine, chlorine, bromine and iodine.

[0184] Examples of the hydrocarbon groups include straight-chain orbranched alkyl groups of 1 to 30 carbon atoms, preferably 1 to 20 carbonatoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl, tert-butyl, neopentyl, n-pentyl and n-hexyl; straight-chainor branched alkenyl groups of 2 to 30 carbon atoms, preferably 2 to 20carbon atoms, such as vinyl, allyl and isopropenyl; straight-chain orbranched alkynyl groups of 2 to 30 carbon atoms, preferably 2 to 20carbon atoms, such as ethynyl and propargyl; cyclic saturatedhydrocarbon groups of 3 to 30 carbon atoms, preferably 3 to 20 carbonatoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl andadamantyl; cyclic unsaturated hydrocarbon groups of 5 to 30 carbonatoms, such as cyclopentadienyl, indenyl and fluorenyl; aryl groups of 6to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as phenyl,benzyl, naphthyl, biphenylyl, terphenylyl, phenanthryl and anthryl; andalkyl-substituted aryl groups, such as tolyl, isopropylphenyl,t-butylphenyl, dimethylphenyl and di-t-butylphenyl.

[0185] In the above hydrocarbon groups, the hydrogen atom may bereplaced with halogen, and examples of these halogenated hydrocarbongroups of 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, includetrifluoromethyl, pentafluorophenyl and chlorophenyl.

[0186] In the above hydrocarbon groups, the hydrogen atom may also bereplaced with another hydrocarbon group, and examples of thesearyl-substituted alkyl groups include benzyl and cumyl.

[0187] Further, the above hydrocarbon groups may have heterocycliccompound residual groups; oxygen-containing groups, such as an alkoxygroup, an aryloxy group, an ester group, an ether group, an acyl group,a carboxyl group, a carbonato group, a hydroxyl group, a peroxy groupand a carboxylic anhydride group; nitrogen-containing groups, such as anamino group, an imino group, an amido group, an imido group, a hydrazinogroup, a hydrazono group, a nitro group, a nitroso group, a cyano group,an isocyano group, a cyanato group, an amidino group, a diazo group andammonium salts derived from an amino group; sulfur-containing groups,such as a mercapto group, a thioester group, a dithioester group, analkylthio group, an arylthio group, a thioacyl group, a thioether group,a thiocyanato group, an isothiocyanato group, a sulfonato ester group, asulfonamido group, a thiocarboxyl group, a dithiocarboxyl group, a sulfogroup, a sulfonyl group, a sulfinyl group and a sulfenyl group;phosphorus-containing groups, such as a phosphido group, a phosphorylgroup, a thiophosphoryl group and a phosphate group; silicon-containinggroups; germanium-containing groups; or tin-containing groups.

[0188] Of the above groups, preferable are straight-chain or branchedalkyl groups of 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms,such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl, t-butyl, neopentyl and n-hexyl; aryl groups of 6 to 30 carbonatoms, preferably 6 to 20 carbon atoms, such as phenyl, naphthyl,biphenylyl, terphenylyl, phenanthryl and anthryl; and substituted arylgroups such as the above aryl groups which are substituted with 1 to 5substituents such as halogen atoms, alkyl or alkoxy groups of 1 to 30carbon atoms, preferably 1 to 20 carbon atoms, and aryl or aryloxygroups of 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms.

[0189] The heterocyclic compound residual groups are cyclic groupscontaining 1 to 5 hetero atoms therein, and particular examples of thehetero atoms include O, N, S, P and B. Particular examples of the cyclicgroups include monocyclic and polycyclic groups of 4 to 7 members, andpreferable are monocyclic and polycyclic groups of 5 to 6 members. Asconcrete examples, there may be enumerated residual groups ofnitrogen-containing compounds such as pyrrole, pyridine, pyrimidine,quinoline and triazine; residual groups of oxygen-containing compoundssuch as furan and pyran; residual groups of sulfur-containing compoundssuch as thiophen; and these residual groups which are furthersubstituted with substituents such as alkyl or alkoxy groups of 1 to 30carbon atoms, preferably 1 to 20 carbon atoms.

[0190] The oxygen-containing groups are groups containing 1 to 5 oxygenatoms therein, but the above-mentioned heterocyclic residual groups areexcluded. Similarly excluded from the oxygen-containing groups aregroups containing a nitrogen atom, a sulfur atom, a phosphorus atom, ahalogen atom or a silicon atom, and having a direct bond of such an atomand an oxygen atom. Examples of the oxygen-containing groups include analkoxy group, an aryloxy group, an ester group, an ether group, an acylgroup, a carboxyl group, a carbonate group, a hydroxyl group, a peroxygroup and a carboxylic anhydride group. Of these, an alkoxy group, anaryloxy group, an acetoxy group, a carbonyl group and a hydroxyl groupare preferable. When these oxygen-containing groups contain carbonatoms, 1 to 30 carbon atoms are preferable, and 1 to 20 carbon atoms aremore preferable.

[0191] The nitrogen-containing groups are groups containing 1 to 5nitrogen atoms therein, but the above-mentioned heterocyclic residualgroups are excluded. Examples of the nitrogen-containing groups includean amino group, an imino group, an amido group, an imido group, ahydrazino group, a hydrazono group, a nitro group, a nitroso group, acyano group, an isocyano group, a cyanato group, an amidino group, adiazo group and ammonium salts derived from an amino group. Of these, anamino group, an imino group, an amido group, an imido group, a nitrogroup and a cyano group are preferable. When these nitrogen-containinggroups contain carbon atoms, 1 to 30 carbon atoms are preferable, and 1to 20 carbon atoms are more preferable.

[0192] The sulfur-containing groups are groups containing 1 to 5 sulfuratoms therein, but the above-mentioned heterocyclic residual groups areexcluded. Examples of the sulfur-containing groups include a mercaptogroup, a thioester group, a dithioester group, an alkylthio group, anarylthio group, a thioacyl group, a thioether group, a thiocyanatogroup, an isothiocyanato group, a sulfonato group, a sulfonamido group,a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonylgroup, a sulfinyl group and a sulfenyl group, a sulfonate group and asulfinate group. Of these, a sulfonate group, a sulfinate group, analkylthio group and an arylthio group are preferable. When thesesulfur-containing groups contain carbon atoms, 1 to 30 carbon atoms arepreferable, and 1 to 20 carbon atoms are more preferable.

[0193] The silicon-containing groups are groups containing 1 to 5silicon atoms therein, and examples thereof include a silyl group, asiloxy group, a hydrocarbon-substituted silyl group and ahydrocarbon-substituted siloxy group. Particular examples of thehydrocarbon-substituted silyl groups include methylsilyl, dimethylsilyl,trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl,diphenylmethylsilyl, triphenylsilyl, dimethylphenylsilyl,dimethyl-t-butylsilyl and dimethyl(pentafluorophenyl)silyl. Of these,preferable are methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl,diethylsilyl, triethylsilyl, dimethylphenylsilyl and triphenylsilyl.Particularly preferable are trimethylsilyl, triethylsilyl,triphenylsilyl and dimethylphenylsilyl. Particular examples of thehydrocarbon-substituted siloxy groups include trimethylsiloxy. Whenthese silicon-containing groups contain carbon atoms, 1 to 30 carbonatoms are preferable, and 1 to 20 carbon atoms are more preferable.

[0194] The phosphorus-containing groups are groups containing 1 to 5phosphorus atoms therein, but the above-mentioned heterocyclic residualgroups are excluded. Examples of the phosphorus-containing groupsinclude a phosphino group, a phosphoryl group, a phosphothioyl group anda phosphono group.

[0195] The boron-containing groups are groups containing 1 to 5 boronatoms therein, but the above-mentioned heterocyclic residual groups areexcluded. Examples of the boron-containing groups include a boronsubstituted with an alkyl group, a boron substituted with an aryl group,a boron halide and a boron halide substituted with an alkyl group.Particular examples of the borons substituted with alkyl groups include(Et)₂B—, (iPr)₂B—, (iBu)₂B—, (nC₅H₁₁)₂B—, C₈H₁₄B— (9-borabicyclononylgroup); particular examples of the borons substituted with aryl groupsinclude (C₆H₅)₂B—; particular examples of the boron halides includeBCl₂—; particular examples of the boron halides substituted with alkylgroups include (Et)BCl— and (iBu)BCl—. In these, Et denotes an ethylgroup, iPr denotes an isopropyl group, and iBu denotes an isobutylgroup.

[0196] Examples of the aluminum-containing groups include AlR₄ (R ishydrogen, an alkyl group, an aryl group which may have a substituent, ahalogen atom or the like).

[0197] Examples of the germanium-containing groups or the tin-containinggroups include groups wherein silicon is replaced with germanium or tinin the above-mentioned silicon-containing groups.

[0198] The heterocyclic compound residual group, the oxygen-containinggroup, the nitrogen-containing group, the sulfur-containing group, theboron-containing group, the germanium-containing group, thetin-containing group, the silicon-containing group and thephosphorus-containing group are each preferably the group wherein thecharacteristic atom group thereof is directly bonded to N, C or a carbonatom in A in the formula (I).

[0199] The above examples of the groups indicated by R¹ to R⁵ are morespecifically described below.

[0200] Of the oxygen-containing groups, preferred examples of the alkoxygroups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,isobutoxy and tert-butoxy; preferred examples of the aryloxy groupsinclude phenoxy, 2,6-dimethylphenoxy and 2,4,6-trimethylphenoxy;preferred examples of the acyl groups include formyl, acetyl, benzoyl,p-chlorobenzoyl and p-methoxybenzoyl; and preferred examples of theester groups include acetyloxy, benzoyloxy, methoxycarbonyl,phenoxycarbonyl and p-chlorophenoxycarbonyl.

[0201] Of the nitrogen-containing groups, preferred examples of theamido groups include acetamido, N-methylacetamido and N-methylbenzamido;preferred examples of the amino groups include alkylamino groups such asmethylamino, dimethylamino, diethylamino, dipropylamino, dibutylaminoand dicyclohexylamino, and arylamino groups or alkylaryl groups such asphenylamino, diphenylamino, ditolylamino, dinaphthylamino andmethylphenylamino; preferred examples of the imido groups includeacetimido and benzimido; and preferred examples of the imino groupsinclude methylimino, ethylimino, propylimino, butylimino andphenylimino.

[0202] Of the sulfur containing groups, preferred examples of thealkylthio groups include methylthio and ethylthio; preferred examples ofthe arylthio groups include phenylthio, methylphenylthio andnaphthylthio; preferred examples of the thioester groups includeacetylthio, benzoylthio, methylthiocarbonyl and phenylthiocarbonyl;preferred examples of sulfonato ester groups include methylsulfonato,ethylsulfonato and phenylsulfonato; and preferred examples of thesulfonamido groups include phenylsulfonamido, N-methylsulfonamido andN-methyl-p-toluenesulfonamido.

[0203] Examples of the sulfonate groups include methylsulfonato,trifluoromethanesulfonato, phenylsulfonato, benzylsulfonato,p-toluenesulfonato, trimethylbenzenesulfonato,triisobutylbenzenesulfonato, p-chlorobenzenesulfonato andpentafluorobenzenesulfonato; examples of the sulfinato groups includemethylsulfinato, phenylsulfinato, benzylsulfinato, p-toluenesulfinato,trimethylbenzenesulfinato and pentafluorobenzenesulfinato.

[0204] Among the phosphorus-containing groups, examples of the phosphinogroups include dimethylphosphino and diphenylphosphino; examples of thephosphoryl groups include methylphosphoryl, isopropylphosphoryl andphenylphosphoryl; examples of the phosphothioyl groups includemethylphosphothioyl, isopropylphosphothioyl and phenylphosphothioyl; andexamples of the phosphono groups include phosphate groups such asdimethylphosphate, diisopropylphosphate and diphenylphosphate, and aphosphoric acid group.

[0205] Two or more groups of R¹ to R⁶, preferably the adjacent groupsthereof, may be bonded to each other to form an aliphatic ring, anaromatic ring, or a hydrocarbon ring containing a hetero atom (e.g., anitrogen atom), which rings may have a substituent respectively.

[0206] The compounds represented by the formula (I) in which R³ and R⁴are bonded to form an aromatic ring are represented by the followingforumula (I-a):

[0207] wherein A, R¹, R² and R⁵ to R¹⁰ have the same meaningsrespectively as those of A and R¹ to R⁶ in the aforesaid formula (I).R¹, R² and R⁵ to R¹⁰ may be the same or different, and two or more ofthem may be bonded to each other to form a ring.

[0208] Among the compounds represented by the above formula (I) or(I-a), particularly preferable are the compounds in which R⁵ is ahydrogen atom.

[0209] The compounds represented by the formula (I) in which R³, R⁴ andR⁵ are bonded to form an aromatic ring and A is a nitrogen atom having asubstituent R⁶ are represented by the following formula (I-b):

[0210] wherein R¹, R², R⁶, R¹¹ to R¹⁵ have the same meanings as those ofR¹ to R⁶ in the above formula (I), R¹, R², R⁶, R¹¹ to R¹⁵ may be thesame or different and two or more of them may be bonded to each other toform a ring.

[0211] Among the compounds represented by the above formula (I-b),particularly preferable are compounds in which R⁶ is a hydrogen atom.

[0212] Examples of such compounds represented by the formula (I) aregiven below.

[0213] The reaction between the transition metal compound (C) and thecompound represented by the formula (I) is carried out, for example, asfollows.

[0214] The transition metal compound (C) and the compound (I) are mixedat a low temperature in the presence of a solvent, and then stirred at atemperature of −78° C. to room temperature, or under reflux, for 1 to 48hours.

[0215] As the solvent, any solvent generally used for such reaction isemployable. Above all, a polar solvent such as ether or tetrahydrofuran(THF), and a hydrocarbon solvent such as toluene are preferable.

[0216] When R⁵ in the formula (I) is a hydrogen atom so that thecompound (I) has an active hydrogen group, the reaction with thetransition metal compound (C) may be conducted after the compound (I)has been contacted with a base to prepare a salt, or after the compound(I) has been contacted with a silicon compound to produce a siliconcompound. As the base used in this case, there may be enumerated basicalkali metal compounds such as n-butyllithium and sodium hydroxide;basic alkali earth metal compounds such as ethylmagnesium bromide; andorganic bases such as triethylamine and pyridine. As the siliconcompound, there may be enumerated alkylsilylchlorides such astrimethylsilylchloride and triethylsilylchloride.

[0217] By the reaction between the transition metal compound (C) and thecompound (I), at least a part of X in the formula (c) is substitutedwith a ligand derived from the compound (I). The number of such ligandscan be adjusted by altering the charge ratio between the transitionmetal compound (C) and the compound (I).

[0218] As the molar ratio between the transition metal compound (C) andthe compound (I) in the reaction, the compound (I) is in an amount ofusually 1 to 6 mol, preferably 1 to 4 mol, based on 1 mol of thetransition metal compound (C).

[0219] In the reaction, two or more kinds of compounds (I) may be used,and a different kind of compound (I) may be added successively duringthe reaction process. In this manner, the compound in which plural kindsof ligands are coordinated to the transition metal can be synthesized.The proportion of ligands coordinated to the transition metal can beadjusted by altering the charge ratio between two or more kinds ofcompounds (I).

[0220] When any of R¹ to R⁴ and R⁶ in the compound (I) is a hydrogenatom, a substituent other than a hydrogen atom may be introduced in anystage of the reaction.

[0221] The composition and structure of the reaction product (Al) can beconfirmed by analyzing through elemental analysis, X-ray crystalstructure analysis, mass spectrum, NMR, IR or the like.

[0222] The thus obtained reaction product (A1) contains theafter-mentioned transition metal compound (IV), and as the case may be,contains also the compound in which a part of X in the formula (c) issubstituted with a ligand derived from the compound (I) (the compound(A1-a)), the unreacted transition metal compound (C), the compound (I)and others.

[0223] After the reaction, the reaction product (A1) may be used in theform of mixture without purification, or with purification bydistillation, recrystallization or the like.

[0224] The metal in the compound contained in the obtained reactionproduct (A1) may be replaced with another transition metal selected fromGroups 4, 5, 6 and 11 of the periodic table by a conventional procedure.

[0225] It is also possible to further convert a substituent other thanthe ligand derived from the compound (I) contained in the compound(A1-a) in the reaction product (A1). Concretely, the residual halogengroup may be converted into a hydrocarbon group, and the amido group maybe converted into a halogen group.

[0226] Reaction Product (A2)

[0227] The catalyst component (A2) is a reaction product of thetransition metal compound (C) represented by the formula (c) and acompound represented by the following formula (II).

[0228] In the above formula (II), D denotes a nitrogen atom or aphosphorus atom.

[0229] Q denotes a nitrogen atom (═N—) or a phosphorus atom (═P—), or acarbon atom substituted with a substitutent R¹³ (═C(R¹³)—).

[0230] S denotes a nitrogen atom (—N═) or a phosphorus atom (—P═), or acarbon atom substituted with a substitutent R¹⁴ (—C(R¹⁴)═).

[0231] T denotes a nitrogen atom (═N—) or a phosphorus atom (═P—), or acarbon atom substituted with a substitutent R (═C(R¹⁵)—).

[0232] R¹¹ to R¹⁶ may be the same or different, and have the samemeanings as those of R¹ to R⁶ in the formula (I).

[0233] In these R¹¹ to R¹⁶, the heterocyclic compound residual group,the oxygen-containing group, the nitrogen-containing group, thesulfur-containing group, the boron-containing group, thegermanium-containing group, the tin-containing group, thesilicon-containing group and the phosphorus-containing group are eachpreferably the group wherein the characteristic atom group thereof isdirectly bonded to N, a carbon atom, a carbon atom in Q, S or T, or D inthe formula (II).

[0234] Two or more groups of R¹¹ to R¹⁶, preferably the adjacent groupsthereof, may be bonded to each other to form an aliphatic ring, anaromatic ring, or a hydrocarbon ring containing a hetero atom (e.g., anitrogen atom), which rings may have a substituent respectively.

[0235] Among the compounds represented by the formula (II), particularlypreferable are the compounds in which R¹⁶ is a hydrogen atom.

[0236] Examples of such compounds represented by the formula (II) aregiven below.

[0237] The reaction between the transition metal compound (C) and thecompound represented by the formula (II) is carried out, for example, asfollows.

[0238] The transition metal compound (C) and the compound (II) are mixedat a low temperature in the presence of a solvent, and then stirred at atemperature of −78° C. to room temperature, or under reflux, for 1 to 48hours.

[0239] As the solvent, the same solvents as previously cited for thepreparation of the reaction product (A1) are employable.

[0240] When R¹⁶ in the formula (II) is a hydrogen atom so that thecompound (II) has an active hydrogen group, the reaction with thetransition metal compound (C) may be conducted after the compound (II)has been contacted with a base to prepare a salt, or after the compound(II) has been contacted with a silicon compound to produce a siliconcompound. As the base and the silicon compound used in this case, thesame ones as previously cited for the preparation of the reactionproduct (A1) may be enumerated.

[0241] By the reaction between the transition metal compound (C) and thecompound (II), at least a part of X in the formula (c) is substitutedwith a ligand derived from the compound (II). The number of such ligandscan be adjusted by altering the charge ratio between the transitionmetal compound (C) and the compound (II).

[0242] As the molar ratio between the transition metal compound (C) andthe compound (II) in the reaction, the compound (II) is in an amount ofusually 1 to 6 mol, preferably 1 to 4 mol, based on 1 mol of thetransition metal compound (C).

[0243] In the reaction, two or more kinds of compounds (II) may be used,and a different kind of compound (II) may be added successively duringthe reaction process. In this manner, the compounds in which pluralkinds of ligands are coordinated to the transition metal can besynthesized. The proportion of ligands coordinated to the transitionmetal can be adjusted by altering the charge ratio between two or morekinds of compounds (II).

[0244] When any of R¹¹ to R¹⁵ in the compound (II) is a hydrogen atom, asubstituent other than a hydrogen atom may be introduced in any stage ofthe reaction.

[0245] The composition and structure of the reaction product (A2) can beconfirmed by analyzing through elemental analysis, X-ray crystalstructure analysis, mass spectrum, NMR, IR or the like.

[0246] The thus obtained reaction product (A2) contains theafter-mentioned transition metal compound (V), and as the case may be,contains also the compound in which a part of X in the formula (c) issubstituted with a ligand derived from the compound (II) (the compound(A2-a)), the unreacted transition compound (C), the compound (II) andothers.

[0247] After the reaction, the reaction product (A2) may be used in theform of mixture without purification, or with purification bydistillation, recrystallization or the like.

[0248] The metal in the compound contained in the obtained reactionproduct (A2) may be replaced with another transition metal selected fromGroups 4, 5, 6 and 11 of the periodic table by a conventional procedure.

[0249] It is also possible to further convert a substituent other thanthe ligand derived from the compound (II) contained in the compound(A2-a) in the reaction product (A2). Concretely, the residual halogengroup may be converted into a hydrocarbon group, and the amido group maybe converted into a halogen group.

[0250] Reaction Product (A3)

[0251] The catalyst component (A3) is a reaction product of thetransition metal compound (C′) represented by the formula (c′) and acompound represented by the following formula (III).

MX_(k)  (c′)

[0252] In the formula (c′), M is a transition metal atom selected fromGroups 3 to 11, preferably Groups 4, 5, 6 and 11, of the periodic table,and specific examples thereof include scandium, yttrium, lanthanum,titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium,molybdenum, tungsten, manganese, rhenium, iron, ruthenium, cobalt,rhodium, nickel, palladium, platinum, copper and silver. Of these,preferable are transition metal atoms selected from Groups 4, 5, 6 and11 of the periodic table, such as titanium, zirconium, hafnium,vanadium, niobium, tantalum, chromium, molybdenum, tungsten, copper andsilver, and more preferable are titanium, vanadium and chromium.

[0253] X and k have the same meanings as those of X and k in the aboveformula (c). When k is 2 or greater, plural groups indicated by X may bethe same or different, and plural groups indicated by X may be bonded toeach other to form a ring.

[0254] In the above formula (III), A denotes an oxygen atom (—O—), asulfur atom (—S—) or a selenium atom (—Se—), or a nitrogen atom having asubstitutent R²⁶ (—N(R²⁶)—).

[0255] R²¹ to R²⁸ may be the same or different, and have the samemeanings as those of R¹ to R6 in the formula (I).

[0256] In these R²¹ to R²⁸, the hetero-containing compound residualgroup, the oxygen-containing group, the nitrogen-containing group, thesulfur-containing group, the boron-containing group, thegermanium-containing group, the tin-containing group, thesilicon-containing group and the phosphorus-containing group are eachpreferably the group wherein the characteristic atom group thereof isdirectly bonded to N, a carbon atom or A in the formula (III).

[0257] Two or more groups of R²¹ to R²⁸, preferably the adjacent groupsthereof, may be bonded to each other to form an aliphatic ring, anaromatic ring, or a hydrocarbon ring containing a hetero atom (e.g., anitrogen atom), which rings may have a substituent respectively.

[0258] Among the compounds represented by the formula (III),particularly preferable are the compounds in which R²⁸ is a hydrogenatom.

[0259] Examples of such compounds represented by the formula (III) aregiven below.

[0260] The reaction between the transition metal compound (C′) and thecompound represented by the formula (III) is carried out, for example,as follows.

[0261] The transition metal compound (C′) and the compound (III) aremixed at a low temperature in the presence of a solvent, and thenstirred at a temperature of −78° C. to room temperature, or underreflux, for 1 to 48 hours.

[0262] As the solvent, the same solvents as previously cited for thepreparation of the reaction product (A1) are employable.

[0263] When R²⁸ in the formula (III) is a hydrogen atom so that thecompound (III) has an active hydrogen group, the reaction with thetransition metal compound (C′) may be conducted after the compound (III)has been contacted with a base to prepare a salt, or after the compound(III) has been contacted with a silicon compound to produce a siliconcompound. As the base and the silicon compound used in this case, thesame ones as previously cited for the preparation of the reactionproduct (A1) may be enumerated.

[0264] By the reaction between the transition metal compound (C′) andthe compound (III), at least a part of X in the formula (c′) issubstituted with a ligand derived from the compound (III). The number ofsuch ligands can be adjusted by altering the charge ratio between thetransition metal compound (C′) and the compound (III).

[0265] As the molar ratio between the transition metal compound (C′) andthe compound (III) in the reaction, the compound (III) is in an amountof usually 1 to 6 mol, preferably 1 to 4 mol, based on 1 mol of thetransition metal compound (C′).

[0266] In the reaction, two or more kinds of compounds (III) may beused, and a different kind of compound (III) may be added successivelyduring the reaction process. In this manner, the compounds in whichplural kinds of ligands are coordinated to the transition metal can besynthesized. The proportion of ligands coordinated to the transitionmetal can be adjusted by altering the charge ratio between two or morekinds of compounds (III).

[0267] When any of R²¹ to R²⁷ in the compound (III) is a hydrogen atom,a substituent other than a hydrogen atom may be introduced in any stageof the reaction.

[0268] The composition and structure of the reaction product (A3) can beconfirmed by analyzing through elemental analysis, X-ray crystalstructure analysis, mass spectrum, NMR, IR or the like.

[0269] The thus obtained reaction product (A3) contains theafter-mentioned transition metal compound (VI), and as the case may be,contains also the compound in which a part of X in the formula (c′) issubstituted with a ligand derived from the compound (III) (the compound(A3-a)), the unreacted transition compound (C′), the compound (III) andothers.

[0270] After the reaction, the reaction product (A3) may be used in theform of mixture without purification, or with purification bydistillation, recrystallization or the like.

[0271] The metal in the compounds contained in the obtained reactionproduct (A3) may be replaced with another transition metal selected fromGroups 4, 5, 6 and 11 of the periodic table by a conventional procedure.

[0272] It is also possible to further convert a substituent other thanthe ligand derived from the compound (III) contained in the compound(A3-a) in the reaction product (A3). Concretely, the residual halogengroup may be converted into a hydrocarbon group, and the amide group maybe converted into a halogen group.

[0273] Transition Metal Compound (A4)

[0274] The transition metal compound (A4) is a compound of a transitionmetal selected from Groups 4, 5, 6 and 11 of the periodic table which isrepresented by the following formula (IV):

[0275] (wherein the dotted line (----) of N----M′ means that acoordinate bond is formed, but a compound having no coordinate bond isalso included in the present invention.)

[0276] In the above formula (IV), M′ has the same meaning as that of M′in the formula (c), and particularly preferable is a titanium atom, avanadium atom, a chromium atom or a copper atom.

[0277] The m is an integer of 1 to 6, preferably an integer of 1 to 4.

[0278] A has the same meaning as that of A in the formula (I).

[0279] R¹ to R⁴ and R⁶ have the same meanings as those of R¹ to R⁶ inthe formula (I).

[0280] Two or more groups of R¹ to R⁴ and R⁶, preferably the adjacentgroups thereof, may be bonded to each other to form an aliphatic ring,an aromatic ring, or a hydrocarbon ring containing a hetero atom (e.g.,a nitrogen atom), which rings may have a substituent respectively. Whenm is 2 or greater, one group of R¹ to R⁴ and R⁶ contained in one ligandmay be bonded to one group of R¹ to R⁴ and R6 contained in anotherligand, and R¹s, R²s, R³s, R⁴s or R6s may be the same or different.

[0281] The n is a number satisfying a valence of M′, and concretely aninteger of 0 to 5, preferably an integer of 1 to 4, more preferably aninteger of 1 to 3.

[0282] X has the same meaning as that of X in the formula (c). When n is2 or greater, the plural groups indicated by X may be the same ordifferent, and the plural groups indicated by X may be bonded to eachother to form a ring.

[0283] The transition metal compound represented by the formula (IV)wherein R³ and R⁴ are bonded to each other to form an aromatic ring isrepresented by the following formula (IV-a).

[0284] In the above formula (IV-a), A, M′, X, m and n have the samemeanings respectively as those of A, M′, X, m and n in the formula (IV).

[0285] R¹, R² and R⁶ to R¹⁰ may be the same or different, and have thesame meanings as those of R¹ to R⁶ in the formula (I). Two or more ofR¹, R² and R⁶ to R¹⁰ may be bonded to each other to form a ring.

[0286] Among the transition metal compounds represented by the formula(IV), the compounds wherein m is 2, and one group of R¹ to R⁴ and R⁶contained in any one ligand is bonded to one group of R¹ to R⁴ and R⁶contained in another ligand are represented, for example, by thefollowing formula (IV-b).

[0287] In the above formula (IV-b), A, M′, X and n have the samemeanings respectively as those of A, M′, X and n in the aforesaidformula (IV).

[0288] R¹ to R⁴ and R6 may be the same or different, and have the samemeanings as those of R¹ to R⁶ in the formula (I). Two or more of R¹ toR⁴ and R⁶ may be bonded to each other to form a ring.

[0289] A′ may be the same as, or different from A, and denotes an oxygenatom (—O—), a sulfur atom (—S—) or a selenium atom (—Se—), or a nitrogenatom having a bonding group R^(6′) (—N(R^(6′))—).

[0290] R^(1′) to R^(4′) and R^(6′) may be the same or different, andhave the same meanings as those of R¹ to R⁶ in the formula (I). Two ormore of R^(1′) to R^(4′) and R^(6′) may be bonded to each other to forma ring. Further, R¹ to R⁴ and R⁶ may be the same as, or different fromR^(1′) to R^(4′) and R^(6′) respectively.

[0291] Y denotes a bonding group or a single bond, in which at least onegroup selected from R¹ to R⁴ is bonded to at least one group selectedfrom R^(1′) to R^(4′). Although there is no specific restriction on thebonding group, it desirably has a structure wherein the main chainconsists of 3 or more atoms, preferably 4 to 20 atoms, more preferably 4to 10 atoms. The bonding group may have a substituent.

[0292] As the bonding group indicated by Y, there may be enumeratedgroups containing at least one element selected from oxygen, sulfur,carbon, nitrogen, phosphorus, silicon, selenium, tin, boron and so on.Examples of such groups include chalcogen atom-containing groups such as—O—, —S— and —Se—; nitrogen or phosphorus atom-containing groups such as—NH—, —N(CH₃)₂—, —PH— and —P(CH₃)₂—; hydrocarbon groups of 1 to 20carbon atoms such as —CH₂—, —CH₂—CH₂— and —C(CH₃)₂—; residual groups ofcyclic unsaturated hydrocarbons of 6 to 20 carbon atoms such as benzene,naphthalene and anthracene; residual groups of heterocyclic compoundshaving 3 to 20 carbon atoms and containing hetero atoms such aspyridine, quinoline, thiophene and furan; silicon atom-containing groupssuch as —SiH₂— and —Si(CH₃)₂—; tin atom-containing groups such as —SnH₂—and —Sn(CH₃) ₂—; and boron atom-containing groups such as —BH—, —B(CH₃)—and —BF—.

[0293] The compounds represented by the formula (IV-b) in which R³ andR⁴ are bonded to R^(3′) and R^(4′) to form an aromatic ring arerepresented by the following forumula (IV-c).

[0294] In the above formula (IV-c), A, M′, X and n have the samemeanings respectively as those of A, M′, X and n in the formula (IV).

[0295] R¹, R² and R⁶ to R¹⁰ may be the same or different, and have thesame meanings as those of R¹ to R⁶ in the formula (I). Two or more ofR¹, R² and R⁶ to R¹⁰ may be bonded to each other to form a ring.

[0296] A′ may be the same as, or different from A, and denotes an oxygenatom (—O—), a sulfur atom (—S—) or a selenium atom (—Se—), or a nitrogenatom having a bonding group R^(6′) (—N(R^(6′))—).

[0297] R^(1′), R^(2′) and R^(6′) to R^(10′) may be the same ordifferent, and have the same meanings as those of R¹ to R⁶ in theformula (I). Two or more of R^(1′), R^(2′) and R^(6′) to R^(10′) may bebonded to each other to form a ring. Further, R¹, R² and R⁶ to R¹⁰ maybe the same as, or different from R^(1′), R^(2′) and R^(6′) to R¹⁰′respectively.

[0298] Y denotes a bonding group or a single bond, in which at least onegroup selected from R¹, R² and R⁶ to R¹⁰ is bonded to at least one groupselected from R^(1′), R^(2′) and R^(6′) to R^(10′). Although there is nospecific restriction on the bonding group, it desirably has a structurewherein the main chain consists of 3 or more atoms, preferably 4 to 20atoms, more preferably 4 to 10 atoms. The bonding group may have asubstituent. As the bonding group indicated by Y, there may beenumerated the same groups as indicated by Y in the formula (IV-b).

[0299] Among the transition metal compounds represented by the aboveformula (IV), compounds in which R³, R⁴ and R⁵ are bonded to form anaromatic ring are represented by the following formula (IV-d).

[0300] In the above formula (IV-d), M′, X, m and n have the samemeanings respectively as those of M′, X, m and n in the formula (IV).

[0301] R¹, R² and R¹¹ to R¹⁵ may be the same or different and have thesame meanings as those of R¹ to R⁶ in the formula (I). Further, two ormore of these R¹, R² and R¹¹ to R¹⁵ may be bonded to each other to forma ring. Examples of the transition metal compounds represented by theformula (IV), (IV-a), (IV-b), (IV-c) and (IV-d) are given below.

[0302] In the case of a compound of a metal of Group 4, the compound inwhich such a metal of Group 4 is replaced with another metal of Group 4may be included in the above examples. Concretely, when a specificexample is a Ti compound, the compound wherein Ti is replaced with Zr orHf can also be enumerated.

[0303] Similarly, in the case of a compound of a metal of Group 5, thecompound in which such a metal of Group 5 is replaced with another metalof Group 5 may be included in the above examples. Concretely, when aspecific example is a V compound, the compound wherein V is replacedwith Nb or Ta can also be enumerated.

[0304] Moreover, in the case of a compound of a metal of Group 6, thecompound in which such a metal of Group 6 is replaced with another metalof Group 6 may be included in the above examples. Concretely, when aspecific example is a Cr compound, the compound wherein Cr is replacedwith Mo or W can also be enumerated.

[0305] Furthermore, in the case of a compound of a metal of Group 11,the compound in which such a metal of Group 11 is replaced with anothermetal of Group 11 may be included in the above examples. Concretely,when a specific example is a Cu compound, the compound wherein Cu isreplaced with Ag or Au can also be enumerated.

[0306] Transition Metal Compound (A5)

[0307] The transition metal compound (A5) is a compound of a transitionmetal selected from Groups 4, 5, 6 and 11 of the periodic table which isrepresented by the following formula (V):

[0308] (wherein the dotted line (----) of N----M′ means that acoordinate bond is formed, but a compound having no coordinate bond isalso included in the present invention.)

[0309] In the above formula (V), M′ has the same meaning as that of M′in the formula (c), and particularly preferable is a titanium atom, avanadium atom, a chromium atom or a copper atom.

[0310] D, Q, S and T have the same meanings respectively as those of D,Q, S and T in the formula (II).

[0311] The m is an integer of 1 to 6, preferably an integer of 1 to 4.

[0312] R¹¹ to R¹⁵ may be the same or different, and have the samemeanings as those of R¹¹ to R¹⁶ in the formula (II). Two or more groupsof R¹¹ to R¹⁵, preferably the adjacent groups thereof, may be bonded toeach other to form an aliphatic ring, an aromatic ring, or a hydrocarbonring containing a hetero atom (e.g., a nitrogen atom), which rings mayhave a substituent respectively. When m is 2 or greater, one group ofR¹¹ to R¹⁵ contained in any one ligand may be bonded to one group of R¹¹to R¹⁵ contained in another ligand, and R¹¹s, R R¹³s, R¹⁴s or R¹⁵s maybe the same or different.

[0313] The n is a number satisfying a valence of M′, and concretely aninteger of 0 to 5, preferably an integer of 1 to 4, more preferably aninteger of 1 to 3.

[0314] X has the same meaning as that of X in the formula (c). When n is2 or greater, the plural groups indicated by X may be the same ordifferent, and the plural groups indicated by X may be bonded to eachother to form a ring.

[0315] Among the compounds represented by the formula (V), the compoundsin which m is 2, and one group of R¹¹ to R¹⁵ contained in any one ligandis bonded one group of R¹¹ to R¹⁵ contained in another ligand arerepresented, for example, by the following forumula (V-a).

[0316] In the above formula (V-a), M′, X, n, D, Q, S and T have the samemeanings respectively as those of M′, X, n, D, Q, S and T in the formula(V).

[0317] R¹¹ to R¹⁵ may be the same or different, and have the samemeanings as those of R¹¹ to R¹⁶ in the formula (II). Two or more of R¹¹to R¹⁵ may be bonded to each other to form a ring.

[0318] D′ may be the same as, or different from D, and denotes anitrogen atom or a phosphorus atom.

[0319] Q′ may be the same as, or different from Q, and denotes anitrogen atom (═N—) or a phosphorus atom (═P—), or a carbon atomsubstituted with a substituent R^(13′) (═C(R^(13′))—).

[0320] S′ may be the same as, or different from S, and denotes anitrogen atom (—N═) or a phosphorus atom (—P═), or a carbon atomsubstituted with a substituent R^(14′) ( C(R^(14′)).

[0321] T′ may be the same as, or different from T, and denotes anitrogen atom (═N—) or a phosphorus atom (═P—), or a carbon atomsubstituted with a substituent R^(15′) (═C(R^(15′))—).

[0322] R^(11′) to R^(15′) may be the same or different, and have thesame meanings as those of R¹ to R⁶ in the formula (I). Two or more ofR^(11′) to R^(15′) may be bonded to each other to form a ring. Further,R¹¹ to R¹⁵ may be the same as, or different from R^(11′) to R^(15′)respectively.

[0323] Y denotes a bonding group or a single bond, in which at least onegroup selected from R¹¹ to R¹⁵ is bonded to at least one group selectedfrom R¹¹ to R¹⁵. Although there is no specific restriction on thebonding group, it desirably has a structure wherein the main chainconsists of 3 or more atoms, preferably 4 to 20 atoms, more preferably 4to 10 atoms. The bonding group may have a substituent. As the bondinggroup indicated by Y, there may be enumerated the same groups asindicated by Y in the formula (IV-b).

[0324] Examples of the transition metal compounds represented by theformula (V) or (V-a) are given below.

[0325] In the case of a compound of a metal of Group 4, the compound inwhich such a metal of Group 4 is replaced with another metal of Group 4may be included in the above examples. Concretely, when a specificexample is a Ti compound, the compound wherein Ti is replaced with Zr orHf can also be enumerated.

[0326] Similarly, in the case of a compound of a metal of Group 5, thecompound in which such a metal of Group 5 is replaced with another metalof Group 5 may be included in the above examples. Concretely, when aspecific example is a V compound, the compound wherein V is replacedwith Nb or Ta can also be enumerated.

[0327] Moreover, in the case of a compound of a metal of Group 6, thecompound in which such a metal of Group 6 is replaced with another metalof Group 6 may be included in the above examples. Concretely, when aspecific example is a Cr compound, the compound wherein Cr is replacedwith Mo or W can also be enumerated.

[0328] Furthermore, in the case of a compound of a metal of Group 11,the compound in which such a metal of Group 11 is replaced with anothermetal of Group 11 may be included in the above examples. Concretely,when a specific example is a Cu compound, the compound wherein Cu isreplaced with Ag or Au can also be enumerated.

[0329] Transition Metal Compound (A6)

[0330] The transition metal compound (A6) is a compound of a transitionmetal selected from Groups 3 to 11 of the periodic table which isrepresented by the following formula (VI):

[0331] (wherein the dotted line (----) of N----M means that a coordinatebond is formed, but a compound having no coordinate bond is alsoincluded in the present invention.)

[0332] In the above formula (VI), M has the same meaning as that of M inthe formula (c′), and preferred is a transition metal atom selected fromGroup 4, 5, 6 and 11 of the periodic table such as titanium, zirconium,hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten,copper and silver, and particularly preferred is titanium, vanadium orchromium.

[0333] The m is an integer of 1 to 6, preferably an integer of 1 to 4.

[0334] A has the same meaning as that of A in the formula (III).

[0335] R²¹to R²⁷ may be the same or different, and have the samemeanings as those of R²¹ to R²⁸ in the formula (III). Two or more groupsof R²¹ to R²⁷, preferably the adjacent groups thereof, may be bonded toeach other to form an aliphatic ring, an aromatic ring, or a hydrocarbonring containing a hetero atom (e.g., a nitrogen atom), which rings mayhave a substituent respectively. When m is 2 or greater, one group ofR²¹ to R²⁷ contained in any one ligand may be bonded to one group of R²¹to R²⁷ contained in another ligand, and R²¹s, R²²s, R²³s, R²⁴s, R²⁵s,R²⁶s or R²⁷s may be the same or different.

[0336] The n is a number satisfying a valence of M, and concretely aninteger of 0 to 5, preferably an integer of 1 to 4, more preferably aninteger of 1 to 3.

[0337] X has the same meaning as that of X in the formula (c)′. When nis 2 or greater, the plural groups indicated by X may be the same ordifferent, and the plural groups indicated by X may be bonded to eachother to form a ring.

[0338] Among the compounds represented by the formula (VI), thecompounds in which m is 2, and one group of R²¹ to R²⁷ contained in anyone ligand is bonded one group of R²¹ to R²⁷ contained in another ligandare represented, for example, by the following formula (VI-a).

[0339] In the above formula (VI-a), A, M, X and n have the same meaningsrespectively as those A, M, X and n in the formula (VI).

[0340] R²¹ to R²⁷ may be the same or different, and have the samemeanings as those of R²¹ to R²⁷ in the formula (III). Two or more of R²¹to R²⁷ may be bonded to each other to form a ring.

[0341] A′ may be the same as, or different from A, and denotes an oxygenatom (—O—), a sulfur atom (—S—) or a selenium atom (—Se—), or a nitrogenatom having a bonding group R^(26′) (—N(R^(26′))—).

[0342] R^(21′) to R^(27′) may be the same or different, and have thesame meanings as those of R¹ to R⁶ in the formula (I). Two or more ofR^(21′) to R^(27′) may be bonded to each other to form a ring. Further,R²¹ to R²⁷ may be the same as, or different from R^(21′) to R^(27′)respectively.

[0343] Y denotes a bonding group or a single bond, in which at least onegroup selected from R²¹ to R²⁷ is bonded to at least one group selectedfrom R^(21′) to R^(27′). Although there is no specific restriction onthe bonding group, it desirably has a structure wherein the main chainconsists of 3 or more atoms, preferably 4 to 20 atoms, more preferably 4to 10 atoms. The bonding group may have a substituent. As the bondinggroup indicated by Y, there may be enumerated the same groups asindicated by Y in the formula (IV-b).

[0344] Examples of the transition metal compounds represented by theformula (VI) or (VI-a) are given below.

[0345] Further, in the above examples, compounds in which the transitionmetal is replaced with another transition metal of the same Group may beenumerated. For example, when a specific example is a Ti compound, thecompound wherein Ti is replaced with Zr or Hf can also be enumerated.

[0346] In processes of the invention, for the above transition metalcompound (A1), (A2), (A4) or (A5), a non-polar olefin and a polar olefinare copolymerized in the presence of a catalyst comprising thesetransition metal compounds and at least one compound (B) selected fromthe group consisting of (B-1) an organometallic compound, (B-2) anorganoaluminum oxy-compound and (B-3) an ionizing ionic compound.

[0347] Further, in the processes of the invention, for the abovetransition metal compound (A0), (A3) or (A6), it is one of the preferredembodiments that a non-polar olefin and a polar olefin are copolymerizedin the presence of a catalyst comprising these transitin metal compoundsand the component (B).

[0348] Next, each compound as the component (B) is described.

[0349] (B-1) Organometallic Compound

[0350] Examples of the organometallic compound (B-1) includeorganometallic compounds containing metals of Group 1, Group 2, Group 12and Group 13 of the periodic table, such as those described below.

[0351] (B-1a) Organoaluminum compound represented by the followingformula:

R^(a) _(m)Al(OR^(b))_(n)H_(p)X_(q)

[0352] wherein R^(a) and R^(b) may be the same or different and are eacha hydrocarbon group of 1 to 15 carbon atoms, preferably 1 to 4 carbonatoms; X is a halogen atom; and m, n, p and q are numbers satisfying theconditions of 0<m≦3, 0≦n<3, 0≦p<3, 0≦q<3 and m+n+p+q=3.

[0353] (B-1b) Alkyl complex compound comprising a metal of Group 1 andaluminum and represented by the following formula:

M²AlR^(a) ₄

[0354] wherein M² is Li, Na or K; and R^(a) is a hydrocarbon group of 1to 15 carbon atoms, preferably 1 to 4 carbon atoms.

[0355] (B-1c) Dialkyl compound containing a metal of Group 2 or Group 12and represented by the following formula:

R^(a)R^(b)M³

[0356] wherein R^(a) and R^(b) may be the same or different and are eacha hydrocarbon group of 1 to 15 carbon atoms, preferably 1 to 4 carbonatoms; and M³ is Mg, Zn or Cd.

[0357] Examples of the organoaluminum compounds (B-1a) include:

[0358] an organoaluminun compound represented by the following formula:

R^(a) _(m)Al(OR^(b))_(3-m)

[0359] wherein R^(a) and R^(b) may be the same or different and are eacha hydrocarbon group of 1 to 15 carbon atoms, preferably 1 to 4 carbonatoms, and m is preferably a number satisfying the condition of 1.5≦m≦3;

[0360] an organoaluminum compound represented by the following formula:

R^(a) _(m)AlX_(3-m)

[0361] wherein R^(a) is a hydrocarbon group of 1 to 15 carbon atoms,preferably 1 to 4 carbon atoms, X is a halogen atom, and m is preferablya number satisfying the condition of 0<m<3;

[0362] an organoaluminum compound represented by the following formula:

R^(a) _(m)AlH_(3-m)

[0363] wherein R^(a) is a hydrocarbon group of 1 to 15 carbon atoms,preferably 1 to 4 carbon atoms, and m is preferably a number satisfyingthe condition of 2≦m<3;

[0364] and

[0365] an organoaluminum compound represented by the following formula:

R^(a) _(m)Al(OR^(b))_(n)X_(q)

[0366] wherein R^(a) and R^(b) may be the same or different and are eacha hydrocarbon group of 1 to 15 carbon atoms, preferably 1 to 4 carbonatoms, X is a halogen atom, and m, n and q are numbers satisfying theconditions of 0<m≦3, 0≦n<3, 0≦q<3 and m+n+q=3.

[0367] Particular examples of the organoaluminum compounds (B-1a)include:

[0368] tri-n-alkylaluminums, such as trimethylaluminum,triethylaluminum, tri-n-butylaluminum, tripropylaluminum,tripentylaluminum, trihexylaluminum, trioctylaluminum andtridecylaluminum;

[0369] branched-chain trialkylaluminums, such as triisopropylaluminum,triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum,tri-2-methylbutylaluminum, tri-3-methylbutylaluminum,tri-2-methylpentylaluminum, tri-3-methylpentylaluminum,tri-4-methylpentylaluminum, tri-2-methylhexylaluminum,tri-3-methylhexylaluminum and tri-2-ethylhexylaluminum;

[0370] tricycloalkylaluminums, such as tricyclohexylaluminum andtricyclooctylaluminum;

[0371] triarylaluminums, such as triphenylaluminum and tritolylaluminum;

[0372] dialkylaluminum hydrides, such as diethylaluminum hydride anddiisobutylaluminum hydride;

[0373] trialkenylaluminums, e.g., those represented by the formula(i—C₄H₉)_(x)Al_(y)(C₅H₁₀)_(z) (wherein x, y and z are each a positivenumber, and z≧2x), such as isoprenylaluminum;

[0374] alkylaluminum alkoxides, such as isobutylaluminum methoxide,isobutylaluminum ethoxide and isobutylaluminum isopropoxide;

[0375] dialkylaluminum alkoxides, such as dimethylaluminum methoxide,diethylaluminum ethoxide and dibutylaluminum butoxide;

[0376] alkylaluminum sesquialkoxides, such as ethylaluminumsesquiethoxide and butylaluminum sesquibutoxide;

[0377] partially alkoxylated alkylaluminums, such as those having anaverage composition represented by R^(a) _(2.5)Al(OR^(b))_(0.5);

[0378] dialkylaluminum aryloxides, such as diethylaluminum phenoxide,diethylaluminum(2,6-di-t-butyl-4-methylphenoxide),ethylaluminumbis(2,6-di-t-butyl-4-methylphenoxide),diisobutylalumium(2,6-di-t-butyl-4-methylphenoxide) andisobutylaluminumbis(2,6-di-t-butyl-4-methylphenoxide);

[0379] dialkylaluminum halides, such as dimethylaluminum chloride,diethylaluminum chloride, dibutylaluminum chloride, diethylaluminumbromide and diisobutylaluminum chloride;

[0380] alkylaluminum sesquihalides, such as ethylaluminumsesquichloride, butylaluminum sesquichloride and ethylaluminumsesquibromide,

[0381] partially halogenated alkylaluminums, such as ethylaluminumdichloride, propylaluminum dichloride and butylaluminum dibromide;

[0382] dialkylaluminum hydrides, such as diethylaluminum hydride anddibutylaluminum hydride;

[0383] partially hydrogenated alkylaluminums, e.g., alkylaluminumdihydrides, such as ethylaluminum dihydride and propylaluminumdihydride; and

[0384] partially alkoxylated and halogenated alkylaluminums, such asethylaluminum ethoxychloride, butylaluminum butoxychloride andethylaluminum ethoxybromide.

[0385] Also employable are compounds analogous to the organoaluminumcompound (B-1a). For example, there can be mentioned organoaluminumcompounds wherein two or more aluminum compounds are combined through anitrogen atom, such as (C₂H₅)₂AlN(C₂H₅)Al(C₂H₅)₂.

[0386] Examples of the compounds (B-1b) include LiAl(C₂H₅)₄ andLiAl(C₇H₁₅)₄.

[0387] Other compounds, also employable as the organometallic compounds(B-1) include methyllithium, ethyllithium, propyllithium, butyllithium,methylmagnesium bromide, methylmagnesium chloride, ethylmagnesiumbromide, ethylmagnesium chloride, propylmagnesium bromide,propylmagnesium chloride, butylmagnesium bromide, butylmagnesiumchloride, dimethylmagnesium, diethylmagnesium, dibutylmagnesium andbutylethylmagnesium.

[0388] Combinations of compounds capable of producing theabove-mentioned organoaluminum compounds in the polymerization system,e.g.,

[0389] a combination of halogenated aluminum and alkyllithium and acombination of halogenated aluminum and alkylmagnesium, are alsoemployable.

[0390] Of the organometallic compounds (B-1), the organoaluminumcompounds are preferable.

[0391] The organometallic compounds (B-1) mentioned above are usedsingly or in combination of two or more kinds.

[0392] (B-2) Organoaluminum Oxy-compound

[0393] The organoaluminum oxy-compound (B-2) may be conventionalaluminoxane or a benzene-insoluble organoaluminum oxy-compound such asexemplified in Japanese Patent Laid-Open Publication No. 78687/1990.

[0394] The conventional aluminoxane can be prepared by, for example, thefollowing processes, and is generally obtained as a hydrocarbon solventsolution.

[0395] (1) An organoaluminum compound such as trialkylaluminum is addedto a hydrocarbon medium suspension of a compound containing adsorptionwater or a salt containing water of crystallization, e.g., magnesiumchloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate,nickel sulfate hydrate or cerous chloride hydrate, to allow theorganoaluminum compound to react with the adsorption water or the waterof crystallization.

[0396] (2) Water, ice or water vapor is allowed to directly act on anorganoaluminum compound such as trialkylaluminum in a medium such asbenzene, toluene, ethyl ether or tetrahydrofuran.

[0397] (3) An organotin oxide such as dimethyltin oxide or dibutyltinoxide is allowed to react with an organoaluminum compound such astrialkylaluminum in a medium such as decane, benzene or toluene.

[0398] The aluminoxane may contain a small amount of an organometalliccomponent. Further, it is possible that the solvent or the unreactedorganoaluminum compound is distilled off from the recovered solution ofaluminoxane and the remainder is redissolved in a solvent or suspendedin a poor solvent for aluminoxane.

[0399] Examples of the organoaluminum compounds used for preparing thealuminoxane include the same organoaluminum compounds as previouslydescribed with respect to the organoaluminum compound (B-1a). Of these,preferable are trialkylaluminums and tricycloalkylaluminums.Particularly preferable is trimethylaluminum.

[0400] The organoaluminum compounds are used singly or in combination oftwo or more kinds.

[0401] Examples of the solvents used for preparing the aluminoxaneinclude aromatic hydrocarbons, such as benzene, toluene, xylene, cumeneand cymene; aliphatic hydrocarbons, such as pentane, hexane, heptane,octane, decane, dodecane, hexadecane and octadecane; alicyclichydrocarbons, such as cyclopentane, cyclohexane, cyclooctane andmethylcyclopentane; petroleum fractions, such as gasoline, kerosine andgas oil; and halogenated products of these aromatic, aliphatic andalicyclic hydrocarbons (e.g., chlorinated or brominated productsthereof). Also employable are ethers such as ethyl ether andtetrahydrofuran. Of the solvents, particularly preferable are aromatichydrocarbons and aliphatic hydrocarbons.

[0402] The benzene-insoluble organoaluminum oxy-compound for use in theinvention is preferably an organoaluminum oxy-compound containing an Alcomponent which is soluble in benzene at 60° C., in an amount of usuallynot more than 10%, preferably not more than 5%, particularly preferablynot more than 2%, in terms of Al atom. That is, the benzene-insolubleorganoaluminum oxy-compound is preferably insoluble or sparingly solublein benzene.

[0403] The organoaluminum oxy-compound is, for example, anorganoaluminum oxy-compound containing boron and represented by thefollowing formula (i):

[0404] wherein R²⁰ is a hydrocarbon group of 1 to 10 carbon atoms; andeach R²¹ may be the same or different and is a hydrogen atom, a halogenatom or a hydrocarbon group of 1 to 10 carbon atoms.

[0405] The organoaluminum compound containing boron and represented bythe formula (i) can be prepared by allowing an alkylboronic acidrepresented by the following formula (ii)

R²⁰—B—(OH)₂  (ii)

[0406] wherein R²⁰ is the same group as described above, to react withan organoaluminum compound in an inert solvent at a temperature of −80°C. to room temperature for 1 minute to 24 hours under an inert gasatmosphere.

[0407] Examples of the alkylboronic acids represented by the formula(ii) include methylboronic acid, ethylboronic acid, isopropylboronicacid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid,n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid,3,5-difluorophenylboronic acid, pentafluorophenylboronic acid and3,5-bis(trifluoromethyl)phenylboronic acid. Of these, preferable aremethylboronic acid, n-butylboronic acid, isobutylboronic acid,3,5-difluorophenylboronic acid and pentafluorophenylboronic acid.

[0408] These alkylboronic acids are used singly or in combination of twoor more kinds.

[0409] Examples of the organoaluminum compounds to be reacted with thealkylboronic acid include the same organoaluminum compounds aspreviously described with respect to the organoaluminum compound (B-1a).Of these, preferable are trialkylaluminums and tricycloalkylaluminums.Particularly preferable are trimethylaluminum, triethylaluminum andtriisobutylaluminum. These organoaluminum compounds are used singly orin combination of two or more kinds.

[0410] The organoaluminum oxy-compounds (B-2) mentioned above are usedsingly or in combination of two or more kinds.

[0411] (B-3) Ionizing Ionic Compound

[0412] The ionizing ionic compound (B-3) includes a compound whichreacts with the reaction product (A1) to form an ion pair, a compoundwhich reacts with the reaction product (A2) to form an ion pair, acompound which reacts with the reaction product (A3) to form an ionpair, a compound which reacts with transition metal compound (A4) toform an ion pair, a compound which reacts with transition metal compound(A5) to form an ion pair, and a compound which reacts with transitionmetal compound (A6) to form an ion pair. Any compound which forms an ionpair by the contact with at least the reaction products and thetransition metal compounds is employable as the compound (B-3).

[0413] Examples of such compounds includes Lewis acids, ionic compounds,borane compounds and carborane compounds described in Japanese PatentLaid-Open Publications No. 501950/1989, No. 502036/1989, No.179005/1991, No. 179006/1991, No. 207703/1991 and No. 207704/1991, andU.S. Pat. No. 5,321,106. A heteropoly compound and an isopoly compoundmay also be employed.

[0414] The Lewis acids are, for example, compounds represented by BR₃ (Ris fluorine or a phenyl group which may have a substituent such asfluorine, methyl or trifluoromethyl). Examples of such compounds includetrifluoroboron, triphenylboron, tris(4-fluorophenyl)boron,tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron,tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron andtris(3,5-dimethylphenyl)boron.

[0415] The ionic compounds are, for example, compounds represented bythe following formula (iii):

[0416] In the above formula, R²² is H⁺, carbonium cation, oxoniumcation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation,ferrocenium cation having a transition metal, or the like.

[0417] R²³ to R²⁶ may be the same or different and are each an organicgroup, preferably an aryl group or a substituted aryl group.

[0418] Examples of the carbonium cations include tri-substitutedcarbonium cations, such as triphenylcarbonium cation,tri(methylphenyl)carbonium cation and tri(dimethylphenyl)carboniumcation.

[0419] Examples of the ammonium cations include trialkylammoniumcations, such as trimethylammonium cation, triethylammonium cation,tripropylammonium cation, tributylammonium cation andtri(n-butyl)ammonium cation; N,N-dialkylanilinium cations, such asN,N-dimethylanilinium cation, N,N-diethylanilinium cation andN,N-2,4,6-pentamethylanilinium cation; and dialkylammonium cations, suchas di(isopropyl)ammonium cation and dicyclohexylammonium cation.

[0420] Examples of the phosphonium cations include triarylphosphoniumcations, such as triphenylphosphonium cation,tri(methylphenyl)phosphonium cation and tri(dimethylphenyl)phosphoniumcation.

[0421] R²² is preferably carbonium cation or ammonium cation,particularly preferably triphenylcarbonium cation, N,N-dimethylaniliniumcation or N,N-diethylanilinium cation.

[0422] Also employable as the ionic compound is a trialkyl-substitutedammonium salt, a N,N-dialkylanilinium salt, a dialkylammonium salt or atriarylphosphonium salt. ExampLes of the trialkyl-substituted ammoniumsalts include triethylammoniumtetra(phenyl)boron,tripropylammoniumtetra(phenyl)boron, tri(n-butylammoniumtetra(phenyl)boron, trimethylammoniumtetra(p-tolyl)boron,trimethylammoniumtetra o-tolyl)boron,tri(n-butyl)ammoniumtetra(pentafluorophenyl)boron,tripropylammoniumtetra(o,p-dimethylphenyl)boron,tri(n-butyl)ammoniumtetra(m,m-dimethylphenyl)boron,tri(n-butyl)ammoniumtetra(p-trifluoromethylphenyl)boron,tri(n-butyl)ammoniumtetra(3,5-ditrifluoromethylphenyl)boron andtri(n-butyl)ammoniumtetra(o-tolyl)boron.

[0423] Examples of the N,N-dialkylanilinium salts includeN,N-dimethylaniliniumtetra(phenyl)boron,N,N-diethylaniliniumtetra(phenyl)boron andN,N-2,4,6-pentamethylaniliniumtetra(phenyl)boron.

[0424] Examples of the dialkylammonium salts includedi(1-propyl)ammoniumtetra(pentafluorophenyl)boron anddicyclohexylammoniumtetra(phenyl)boron Further employable as the ioniccompounds are triphenylcarbeniumtetrakis(pentafluorophenyl)borate,N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate,ferroceniumtetra(pentafluorophenyl)borate,triphenylcarbeniumpentaphenylcyclopentadienyl complex,N,N-diethylaniliniumpentaphenylcyclopentadienyl complex and a boroncompound represented by the formula (iv):

[0425] wherein Et is an ethyl group, or the formula (v):

[0426] Examples of the borane compounds include:

[0427] decaborane;

[0428] salts of anions, such as

[0429] bis[tri(n-butyl)ammonium]nonaborate,

[0430] bis[tri(n-butyl)ammonium]decaborate,

[0431] bis[tri(n-butyl)ammonium]undecaborate,

[0432] bis[tri(n-butyl)ammonium]dodecaborate,

[0433] bis[tri(n-butyl)ammonium]decachlorodecaborate and

[0434] bis[tri(n-butyl)ammonium]dodecachlorododecaborate; and

[0435] salts of metallic borane anions, such astri(n-butyl)ammoniumbis(dodecahydridododecaborate)cobaltate (III) andbis [tri(n-butyl)ammonium]bis-(dodecahydridododecaborate)nickelate(III).

[0436] Examples of the carborane compounds include:

[0437] salts of anions, such as 4-carbanonaborane,1,3-dicarbanonaborane, 6,9-dicarbadecaborane,dodecahydrido-l-phenyl-l,3-dicarbanonaborane,dodecahydrido-l-methyl-l,3-dicarbanonaborane,undecahydrido-l,3-dimethyl-l,3-dicarbanonaborane,7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane,undecahydrido-7,-dimethyl-7, 8-dicarbaundecaborane,dodecahydrido-11-methyl-2,7-dicarbaundecaborane, tri(n-butyl)ammonium-1-carbadecaborate, tri(n-butyl)ammonium-1-carbaundecaborate, tri(n-butyl)ammonium-1-carbadodecaborate, tri(n-butyl)ammonium-1-trimethylsilyl-1-carbadecaborate, tri(n-butyl)ammoniumbromo-1-carbadodecaborate, tri(n-butyl)ammonium-6-carbadecaborate, tri(n-butyl)ammonium-6-carbadecaborate,tri(n-butyl)ammonium-7-carbaundecaborate,tri(n-butyl)ammonium-7,8-dicarbaundecaborate,tri(n-butyl)ammonium-2,9-dicarbaundecaborate,tri(n-butyl)ammoniumdodecahydrido-8-me thyl-7,9-dicarbaundecaborate,tri(n-butyl)ammoniumundecahydrido-8-ethyl-7,9-dicarbaundecaborate,tri(n-butyl)ammoniumundecahydrido-8-butyl-7,9-dicarbaundecaborate,tri(n-butyl)ammoniumundecahydrido-8-allyl-7,9-dicarbaundecaborate,tri(n-butyl)ammoniumundecahydrido-9-trimethylsilyl-7,8-dicarbaundecaborateand tri(n-butyl)ammoniumundecahydrido-4,6-dibromo-7-carbaundecaborate;and

[0438] salts of metallic carborane anions, such astri(n-butyl)ammoniumbis(nonahydrido-1,3-dicarbanonaborate)cobaltate(III),tri(n-butyl)ammoniumbis(undecahydrido-7,8-dicarbaundecaborate)ferrate(III),tri(n-butyl)ammoniumbis(undecahydrido-7,8-dicarbaundecaborate)cobaltate(III),tri(n-butyl)ammoniumbis(undecahydrido-7,8-dicarbaundecaborate)nickelate(III),tri(n-butyl)ammoniumbis(undecahydrido-7,8-dicarbaundecaborate)cuprate(III),tri(n-butyl)ammoniumbis(undecahydrido-7,8-dicarbaundecaborate)aurate(III),tri(n-butyl)ammoniumbis(nonahydrido-7,8-dimethyl-7,8-dicarbaundecaborate)ferrate(III),tri(n-butyl)ammoniumbis(nonahydrido-7,8-dimethyl-7,8-dicarbaundecaborate)chromate(III),tri(n-butyl)ammoniumbis(tribromooctahydrido-7,8-dica-rbaundecaborate)cobaltate(III),tris[tri(n-butyl)ammonium]bis(undecahydrido-7-carbaundecaborate)chromate(III),bis[tri(n-butyl)ammonium]bis(undecahydrido-7-carbaundecaborate)manganate(IV),bis[tri(n-butyl)ammonium]bis(undecahydrido-7-carbaundecaborate)cobaltate(III)andbis[tri(n-butyl)ammonium]bis(undecahydrido-7-carbaundecaborate)nickelate(IV).

[0439] The heteropoly compound comprises an atom of silicon, phosphorus,titanium, germanium, arsenic or tin and one or more atoms selected fromvanadium, niobium, molybdenum and tungsten. Examples of such compoundsinclude phosphovanadic acid, germanovanadic acid, arsenovanadic acid,phosphoniobic acid, germanoniobic acid, silicomolybdic acid,phosphomolybdic acid, titanomolybdic acid, germanomolybdic acid,arsenomolybdic acid, stannomolybdic acid, phosphotungstic acid,germanotungstic acid, stannotungstic acid, phosphomolybdovanadic acid,phosphotungstovanadic acid, germanotaungstovanadic acid,phosphomolybdotungstovanadic acid, germanomolybdotungstovanadic acid,phosphomolybdotungstic acid, phosphomolybdoniobic acid, metallic saltsof these acids, specifically, salts of these acids, for example withmetals of Group 1 or 2 of the periodic table such as lithium, sodium,potassium, rubidium, cesium, beryllium, magnesium, calcium, strontiumand barium, organic salts of the above acids such as triphenylethylsalt, and isopoly compounds.

[0440] These heteropoly compounds and isopoly compounds may be usedsingly or in combination of two or more kinds.

[0441] The ionizing ionic compounds (B-3) mentioned above may be usedsingly or in combination of two or more kinds.

[0442] (C) Carrier

[0443] In the present invention, the below-described carrier (C) canoptionally be used by supporting at least one component selected fromthe above-mentioned reaction products (A1) to (A3) and transition metalcompounds (A0) and (A4) to (A6) (referred to as “Component A”hereinafter) and/or at least one compound selected from theorganometallic compound (B-1), the organoaluminum oxy-compound (B-2) andthe ionizing ionic compound (B-3) (referred to as “Compound B”hereinafter).

[0444] The carrier (C) optionally used in the invention is an inorganicor organic compound in the form of granular or particulate solid. As theinorganic compounds, porous oxides, inorganic chlorides, clay, clayminerals or ion-exchange layered compounds are preferable.

[0445] Examples of the porous oxides include SiO₂, Al₂O₃, MgO, ZrO,TiO₂, B₂O₃, CaO, ZnO, BaO, ThO₂, and complex compounds or mixturescontaining these oxides, such as natural or synthetic zeolite, SiO₂—MgO,SiO₂—Al₂O₃, SiO₂—TiO₂, SiO₂—V₂O₅, SiO₂—Cr₂O₃ and SiO₂—TiO₂—MgO. Ofthese, preferable are compounds containing SiO₂ and/or Al₂O₃ as the maincomponent.

[0446] The inorganic oxides may contain small amounts of carbonate,sulfate, nitrate and oxide components, such as Na₂CO₃, K₂CO₃, CaCO₃,MgCO₃, Na₂SO₄, Al₂(SO₄)₃, BaSO₄, KNO₃, Mg(NO₃)₂, Al(NO₃) ₃, Na₂O, K₂Oand Li₂O.

[0447] Although the porous oxides differ in their properties dependingupon the type and the preparation process thereof, the carrierpreferably used in the invention has a particle diameter of 10 to 300μm, preferably 20 to 200 μm, a specific surface area of 50 to 1,000m²/g, preferably 100 to 700 m²/g, and a pore volume of 0.3 to 3.0 cm³/g.If necessary, the carrier may be calcined at 100 to 1,000° C.,preferably 150 to 700° C., prior to use.

[0448] Examples of the inorganic chlorides employable in the inventioninclude MgCl₂, MgBr₂, MnCl₂ and MnBr₂. The inorganic chloride may beused as it is, or may be used after pulverized by, for example, a ballmill or an oscillating mill. The inorganic chloride may also be used asfine particles of a obtained by dissolving the inorganic chloride in asolvent such as alcohol and then precipitating using a precipitant.

[0449] The clay employable as a carrier in the invention is generallycomposed mainly of clay minerals. The ion-exchange layered-compoundsemployable as a carrier in the invention is compounds having a crystalstructure wherein planes formed by ionic bonding or the like arelaminated in parallel to one another with a weak bond strength, and theions contained therein are exchangeable. Most of clay minerals areion-exchange layered compounds. The clay, the clay minerals and theion-exchange layered compounds employable in the invention are notlimited to natural ones but include synthetic ones.

[0450] Examples of such clay, clay minerals and ion-exchange layeredcompounds include clay, clay minerals and ion crystalline compoundshaving layered crystal structures such as hexagonal closest packingtype, antimony type, CdCl₂ type and CdI₂ type.

[0451] Particular examples of the clay and the clay minerals includekaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite,pyrophyllite, mica, montmorillonite, vermiculite, chlorite,palygorskite, kaolinite, nacrite, dickite and halloysite. Particularexamples of the ion-exchange layered compounds include crystalline acidsalts of polyvalent metals, such as α-Zr(HAsO₄)₂.H₂O, α-Zr(HPO₄)₂,α-Zr(KPO₄)₂.3H₂O, α-Ti(HPO₄)₂, α-Ti(HasO₄)₂.H₂O, α-Sn(HPO₄)₂.H₂O,γ-Zr(HPO₄)₂, γ-Ti(HPO₄)₂ and γ-Ti(NH₄PO₄)₂.H₂,

[0452] The clay, the clay minerals and the ion-exchange layeredcompounds are preferably those having a pore volume, as measured onpores having a radius of not less than 20 Å by a mercury penetrationmethod, of not less than 0.1 cc/g, and are particularly preferably thosehaving a pore volume of 0.3 to 5 cc/g. The pore volume is measured onthe pores having a radius of 20 to 3×10⁴ Å by a mercury penetrationmethod using a mercury porosimeter.

[0453] If a compound having a pore volume, as measured on pores having aradius of not less than 20 Å, of less than 0.1 cc/g is used as thecarrier, high polymerization activity tends to be hardly obtained.

[0454] It is also preferable that the clay and the clay minerals to beused in the invention are subjected to chemical treatments. Any ofsurface treatments, for example, to remove impurities attached to thesurface and to influence on the crystal structure of the clay, areemployable. Examples of such chemical treatments include acid treatment,alkali treatment, salt treatment and organic substance treatment. Theacid treatment can contribute to not only removing impurities from thesurface but also eluting cations such as Al, Fe and Mg present in thecrystal structure to increase the surface area. The alkali treatment candestroy crystal structure of clay to bring about change in the structureof the clay. The salt treatment and the organic substance treatment canproduce, for example, ionic composites, molecular composites, or organicderivative to change the surface area or the distance between layers.

[0455] The ion-exchange layered compound for use in the invention may bea layered compound in which the exchangeable ions between layers havebeen exchanged with other large and bulky ions utilizing ion exchangeproperties to enlarge the distance between the layers. The bulky ionplays a pillar-like roll to support the layer structure and is generallycalled a “pillar”. Introduction of other substances between layers of alayered compound is called “intercalation”. Examples of the guestcompounds to be intercalated include cationic inorganic compounds, suchas TiCl₄ and ZrCl₄; metallic alkoxides, such as Ti(OR)₄, Zr(OR)₄,PO(OR)₃ and B(OR)₃ (R is a hydrocarbon group or the like); and metallichydroxide ions, such as [Al₁₃O₄(OH)₂₄]⁷⁺, [Zr₄(OH)₁₄]²⁺ and[Fe₃O(OCOCH₃)₆].

[0456] The compounds mentioned above may be used singly or incombination of two or more kinds.

[0457] The intercalation of the compounds may be carried out in thepresence of polymers obtained by hydrolysis of metallic alkoxides suchas Si(OR)₄, Al(OR)₃ and Ge(OR)₄ (R is a hydrocarbon group or the like)or in the presence of colloidal inorganic compounds such as SiO₂.Examples of the pillars include oxides produced by intercalation of theabove-mentioned metallic hydroxide ions between layers, followed bydehydration under heating.

[0458] The clay, clay minerals and ion-exchange layered compoundsmentioned above may be used as they are, or may be used after they aresubjected to a treatment of ball milling, sieving or the like. Moreover,they may be used after they are subjected to water adsorption ordehydration under heating. The clay, clay minerals and ion-exchangelayered compounds may be used singly or in combination of two or morekinds.

[0459] Of the above-mentioned materials, preferable are clay and clayminerals, and particularly preferable are montmorillonite, vermiculite,hectorite, tenorite and synthetic mica.

[0460] The organic compound is, for example, a granular or particulatesolid compound having a particle diameter of 10 to 300 μm. Examples ofsuch compounds include (copolymers produced using an (α-olefin of 2 to14 carbon atoms such as ethylene, propylene, 1-butene or4-methyl-1-pentene as a main ingredient, (co)polymers produced usingvinylcyclohexane or styrene as a main ingredient, and modified productsthereof.

[0461] (D) Organic Compound Component

[0462] In the polymerization of the invention, the below-describedspecific organic compound component (D) may be optionally used.

[0463] The organic compound component (D) is optionally used to improvepolymerizability and properties of the resulting polymer. Examples ofthe organic compounds include alcohols, phenolic compounds, carboxylicacids, carboxylic acid esters, phosphorus compounds, sulfonates andhalogenated hydrocarbons.

[0464] As the alcohols and the phenolic compounds, those represented byR³¹—OH (R³¹ is a hydrocarbon group of 1 to 50 carbon atoms or ahalogenated hydrocarbon group of 1 to 50 carbon atoms) are generallyemployed. Preferable alcohols are those wherein R³¹ is a halogenatedhydrocarbon group. Preferable phenolic compounds are preferably thosewherein the α,α-positions to the hydroxyl group are substituted withhydrocarbon groups of 1 to 20 carbon atoms.

[0465] As the carboxylic acids, those represented by R³²—COOH (R³² is ahydrocarbon group of 1 to 50 carbon atoms or a halogenated hydrocarbongroup of 1 to 50 carbon atoms, preferably a halogenated hydrocarbongroup of 1 to 50 carbon atoms) are generally employed.

[0466] As the carboxylic acid esters, alkyl or aryl esters of thecarboxylic acids represented by R³²—COOH are generally employed. Ofthese, desirable are carboxylic acid esters having halogenatedhydrocarbon groups such as n-butyl perchlorocrotonate and ethyltrichloroacetate for the purpose to improve polymerizability.

[0467] As the phosphorus compounds, phosphoric acids having P—O—H bond,phosphates having P—OR bond or P═O bond and phosphine oxide compoundsare preferably employed.

[0468] The sulfonates used in the invention are those represented by thefollowing formula:

[0469] In the above formula, M is an element of Group 1 to Group 14 ofthe periodic table.

[0470] R³³ is hydrogen, a hydrocarbon group of 1 to 20 carbon atoms or ahalogenated hydrocarbon group of 1 to 20 carbon atoms.

[0471] X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to20 carbon atoms or a halogenated hydrocarbon group of 1 to 20 carbonatoms.

[0472] m is an integer of 1 to 7, and 1≦n≦7.

[0473] As halogenated hydrocarbons, chloroform and carbon tetrachlorideare exemplified.

[0474] Other Transition Metal Compounds

[0475] In the polymerization of the present invention, transition metalcompounds other than the above mentioned transition metal compound (A0)and (A4) to (A6) can be used in combination.

[0476] Examples of the other transition metal compounds include thefollowing compounds.

[0477] (a-1) Transition metal imide compound represented by thefollowing formula:

[0478] In the above formula, M is a transition metal atom of Group 8 toGroup 10 of the periodic table, preferably nickel, palladium orplatinum.

[0479] R³¹ to R³⁴ may be the same or different and are each ahydrocarbon group of 1 to 50 carbon atoms, a halogenated hydrocarbongroup of 1 to 50 carbon atoms, a hydrocarbon-substituted silyl group, ora hydrocarbon group substituted with a substituent containing at leastone element selected from nitrogen, oxygen, phosphorus, sulfur andsilicon.

[0480] Two or more of the groups indicated by R³¹ to R³⁴, preferablyadjacent groups, may be bonded to each other to form a ring.

[0481] q is an integer of 0 to 4.

[0482] X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbonatoms, an oxygen-containing group, a sulfur-containing group, asilicon-containing group or a nitrogen-containing group. When q is 2 orgreater, plural groups indicated by X may be the same or different.

[0483] (a-2) Transition metal amide compound represented by thefollowing formula:

[0484] In the above formula, M is a transition metal atom of Group 3 toGroup 6 of the periodic table, preferably titanium, zirconium orhafnium.

[0485] R′ and R″ may be the same or different and are each a hydrogenatom, a hydrocarbon group of 1 to 50 carbon atoms, a halogenatedhydrocarbon group of 1 to 50 carbon atoms, a hydrocarbon-substitutedsilyl group, or a substituent having at least one element selected fromnitrogen, oxygen, phosphorus, sulfur and silicon.

[0486] m is an integer of 0 or 2.

[0487] n is an integer of 1 to 5

[0488] A is an atom of Group 13 to Group 16 of the periodic table,specifically boron, carbon, nitrogen, oxygen, silicon, phosphorus,sulfur, germanium, selenium, tin or the like, preferably carbon orsilicon. When n is 2 or greater, plural of A may be the same ordifferent.

[0489] E is a substituent having at least one element selected fromcarbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boronand silicon. When m is 2, two of E may be the same or different, or maybe bonded to each other to form a ring.

[0490] p is an integer of 0 to 4.

[0491] X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbonatoms, an oxygen-containing group, a sulfur-containing group, asilicon-containing group or a nitrogen-containing group. When p is 2 orgreater, plural groups indicated by X may be the same or different.

[0492] X is preferably a halogen atom, a hydrocarbon group of 1 to 20carbon atoms or a sulfonato group.

[0493] (a-3) Transition metal diphenoxy compound represented by thefollowing formula:

[0494] In the above formula, M is a transition metal atom of Group 3 toGroup 11 of the periodic table.

[0495] l and m are each an integer of 0 or 1.

[0496] A and A′ are each a hydrocarbon group of 1 to 50 carbon atoms, ahalogenated hydrocarbon group of 1 to 50 carbon atoms, or a hydrocarbongroup or a halogenated hydrocarbon group of 1 to 50 carbon atoms eachhaving a substituent containing oxygen, sulfur or silicon; and A and A′may be the same or different.

[0497] B is a hydrocarbon group of 0 to 50 carbon atoms, a halogenatedhydrocarbon group of 1 to 50 carbon atoms, a group represented by R¹R²Z,oxygen or sulfur. R¹ and R² are each a hydrocarbon group of 1 to 20carbon atoms or a hydrocarbon group of 1 to 20 carbon atoms containingat least one hetero atom, and Z is a carbon atom, a nitrogen atom, asulfur atom, a phosphorus atom or a silicon atom.

[0498] p is a number satisfying a valence of M.

[0499] X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbonatoms, an oxygen-containing group, a sulfur-containing group, asilicon-containing group or a nitrogen-containing group. When p is 2 orgreater, plural groups X may be the same or different or may be bondedto each other to form a ring.

[0500] (a-4) Transition metal compound represented by the followingformula and comprising a ligand having cyclopentadienyl skeletoncontaining at least one hetero atom:

[0501] In the above formula, M is a transition metal atom of Group 3 toGroup 11 of the periodic table.

[0502] X is an atom of Group 13, Group 14 or Group 15 of the periodictable, and at least one X is an element other than carbon.

[0503] a is 0 or 1.

[0504] Each R may be the same or different and is a hydrogen atom, ahalogen atom, a hydrocarbon group, a halogenated hydrocarbon group, ahydrocarbon-substituted silyl group, or a hydrocarbon group substitutedwith a substituent containing at least one element selected fromnitrogen, oxygen, phosphorus, sulfur and silicon. Two or more of R maybe bonded to each other to form a ring.

[0505] b is an integer of 1 to 4. When b is 2 or greater, groups[((R)_(a))₅-X₅] may be the same or different, and Rs may be bridged toeach other.

[0506] c is a number satisfying a valence of M.

[0507] Y is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbonatoms, an oxygen-containing group, a sulfur-containing group, asilicon-containing group or a nitrogen-containing group. When c is 2 orgreater, plural groups indicated by Y may be the same or different, andmay be bonded to each other to form a ring.

[0508] (a-5) Transition metal compound represented by the formulaPB(Pz)₃MX_(n).

[0509] In the above formula, M is a transition metal atom of Group 3 toGroup 11 of the periodic table.

[0510] R is a hydrogen atom, a hydrocarbon group of 1 to 20 carbon atomsor a halogenated hydrocarbon group of 1 to 20 carbon atoms.

[0511] Pz is a pyrazolyl group or a substituted pyrazolyl group.

[0512] n is a number satisfying a valence of M.

[0513] X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to20 carbon atomsr a halogenated hydrocarbon group of 1 to 20 carbonatoms, an oxygen-containing group, a sulfur-containing group, asilicon-containing group or a nitrogen-containing group. When n is 2 orgreater, plural groups indicated by X may be the same or different ormay be bonded to each other to form a ring.

[0514] (a-6) Transition metal compound represented by the followingformula:

[0515] In the above formula, Y¹ and Y³ may be the same or different andare each an element of Group 15 of the periodic table, and y2 is anelement of Group 16 of the periodic table.

[0516] R⁴¹ to R⁴⁸ may be the same or different, they are each a hydrogenatom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, ahalogenated hydrocarbon group of 1 to 20 carbon atoms, anoxygen-containing group, a sulfur-containing group or asilicon-containing group, and two or more of them may be bonded to eachother to form a ring.

[0517] (a-7) Compound comprising a compound represented by the followingformula and a transition metal atom of Group 8 to Group 10 of theperiodic table:

[0518] In the above formula, R⁵¹ to R⁵⁴ may be the same or different,they are each a hydrogen atom, a halogen atom, a hydrocarbon group of 1to 20 carbon atoms or a halogenated hydrocarbon group of 1 to 20 carbonatoms, and two or more of them may be bonded to each other to form aring.

[0519] (a-8) Transition metal compound represented by the followingformula:

[0520] In the above formula, M is a transition metal atom of Group 3 toGroup 11 of the periodic table.

[0521] m is an integer of 0 to 3.

[0522] n is an integer of 0 or 1.

[0523] p is an integer of 1 to 3.

[0524] q is a number satisfying a valence of M.

[0525] R⁶¹ to R68 may be the same or different, they are each a hydrogenatom, a halogen atom, a hydrocarbon group of 1 to 20 carbon atoms, ahalogenated hydrocarbon group of 1 to 20 carbon atoms, anoxygen-containing group, a sulfur-containing group, a silicon-containinggroup or a nitrogen-containing group, and two or more of them may bebonded to each other to form a ring.

[0526] X is a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbonatoms, an oxygen-containing group, a sulfur-containing group, asilicon-containing group or a nitrogen-containing group. When q is 2 orgreater, plural groups indicated by X may be the same or different ormay be bonded to each other to form a ring.

[0527] Y is a group to bridge a boratabenzene ring and is carbon,silicon or germanium.

[0528] A is an element of Group 14, Group 15 or Group 16 of the periodictable.

[0529] (a-9) Transition metal compound other than the aforesaid compound(a-4) and containing a ligand having cyclopentadienyl skeleton.

[0530] (a-10) Compound containing magnesium, titanium and halogen asessential ingredients

[0531] Copolymerization

[0532] In the process for producing a polar olefin copolymer accordingto the present invention, a non-polar olefin and a polar olefin arecopolymerized in the presence of a catalyst comprising the aforesaidcomponents (A) and (B). FIG. 1 shows an example of the preparationprocess of the olefin polymerization catalyst used in the presentinvention.

[0533] Non-polar olefin means the unsaturated hydrocarbon consisting ofcarbon atoms and hydrogen atoms only. Examples of the non polar olefinsinclude α-olefins of 2 to 20 carbon atoms such as ethylene, propylene,1-butene, 1-pentene, 3-methyl-l-butene, 1-hexene, 4-methyl-1-pentene,3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,1-hexadecene, 1-octadecene and 1-eicocene; cycloolefins of 3 to 20carbon atoms such as cyclopentene, cycloheptene, norbornene,5-methyl-2-norbornene and tetracyclododecene; dienes or polyenes whichare cyclic or chain compounds having two or more double bonds, andhaving 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms, such asbutadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene,1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene,1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene,1,7-octadiene, ethylidene norbornene, vinyl norbornene,dicyclopentadiene, 7-methyl-1,6-octadiene,4-ethylidene-8-methyl-1,7-nonadiene and 5,9-dimethyl-1,4,8-decatriene;aromatic vinyl compounds such as styrene, o-methylstyrene,m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene,m-ethylstyrene and p-ethylstyrene; and vinylcyclohexane. Of these,preferable are α-olefins, and particularly preferable is ethylene.

[0534] The polar olefins of the present invention are unsaturatedhydrocarbons having polar groups. Examples thereof include:

[0535] unsaturated carboxylic acids such as acrylic acid, 3-butenoicacid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoicacid, 8-nonenoic acid, 9-decenoic acid, lO-undecenoic acid,11-dodecenoic acid, 12-tridecenoic acid, 13-tetradecenoic acid,14-pentadecenoic acid, 15-hexadecenoic acid, 16-heptadecenoic acid,17-octadecenoic acid, 18-nonadecenoic acid, 19-eicosenoic acid,20-heneicosanoic acid, 21-docosenoic acid, 22-tricosanoic acid,methacrylic acid, 2-methyl-pentenoic acid, 2,2-dimethyl-3-butenoic acid,2,2-dimethyl-4-pentenoic acid, 3-vinyl-benzoic acid, 4-vinyl-benzoicacid, 2,6-heptadiene acid, 2-(4-isopropylbenzylidene)-4-pentenoic acid,allylmalonic acid, 2-(10-undecenyl)malonic acid, fumaric acid, itaconicacid, bicyclo[2.2.1]-5-heptene-2-carboxylic-acidand-bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid,

[0536] metallic salts thereof such as sodium salt, potassium salt,lithium salt, zinc salt, magnesium salt and calcium salt,

[0537] unsaturated carboxylic esters thereof such as methyl ester, ethylester, n-propyl ester, isopropyl ester, n-butyl ester, isobutyl esterand (5-norbornene-2-yl)ester (when the unsaturated carboxylic acid isdicarboxylic acid, both monoester and diester may be included.), and

[0538] unsaturated carboxylic acid amides thereof such as N,N-dimethylamide (when the unsaturated carboxylic acid is dicarboxylic acid, bothmonoamide and diamide may be included.);

[0539] unsaturated carboxylic anhydrides such as maleic anhydride,itaconic anhydride, succinic anhydride, isobutenyl succinic anhydride,(2,7-octadiene-1-yl)succinic anhydride, tetrahydrophtalic anhydride andbicyclo[2.2.1]-5-heptene-2,3-dicarboxylic anhydride;

[0540] vinyl esters such as vinyl acetate, vinyl propionate, vinylcaproate, vinyl caprate, vinyl laurate, vinyl stearate and vinyltrifluoroacetate;

[0541] halogenated olefins such as vinyl chloride, vinyl fluoride, allylbromide, allyl chloride and allyl fluoride;

[0542] silylated olefins such as allyltrimethylsilane,diallyldimethylsilane, 3-butenyltrimethylsilane, allyltriisopropylsilaneand allyltriphenylsilane;

[0543] unsaturated nitriles such as acrylonitrile, 2-cyanobicyclo[2.2.1]-5-heptene and 2,3-dicyanobicyclo [2.2.1]-5-heptene;

[0544] unsaturated alcohol compounds such as allylalcohol, 3-butenol,4-pentenol, 5-hexenol, 6-heptenol, 7-octenol, 8-nonenol, 9-decenol,10-undecenol, 11-dodecenol and 12-tridecenol, and unsaturated estersthereof such as acetate, benzoate, propionate, caproate, caprate,laurate and stearate;

[0545] substituted phenols such as vinyl phenol and allyl phenol;

[0546] unsaturated ethers such as methylvinyl ether, ethylvinyl ether,allylmethyl ether, allylpropyl ether, allylbutyl ether, allylmethallylether, methoxy styrene and ethoxy styrene;

[0547] unsaturated epoxides such as butadiene monooxide,1,2-epoxy-7-octene and 3-vinyl-7-oxabicyclo[4.1.0]heptane, unsaturatedaldehydes such as acrolein and undecenal and unsaturated acetals thereofsuch as dimethyl acetal and diethyl acetal;

[0548] unsaturated ketones such as methylvinyl ketone, ethylvinylketone, allylmethyl ketone, allylethyl ketone, allylpropyl ketone,allylbutyl ketone and allylbenzyl ketone and unsaturated acetals thereofsuch as dimethyl acetal and diethyl acetal;

[0549] unsaturated thioethers such as allylmethyl sulfide, allylphenylsulfide, allylisopropyl sulfide, allyl-n-propyl sulfide and4-pentenylphenyl sulfide; unsaturated sulfoxides such as allylphenylsulfoxide; and

[0550] unsaturated sulfones such as allylphenyl sulfone; unsaturatedphosphines such as allyldiphenyl phosphine; and unsaturated phosphineoxides such as allyldiphenyl phosphine oxide.

[0551] Further, unsaturated hydrocarbons having two or more of the abovementioned polar groups are employable. Examples thereof includevinylbenzoic acid, methylvinylbenzoate, vinylbenzylacetate,hydroxystyrene, 4-(3-butenyloxy)methyl benzoate, allyltrifluoroacetate,o-chlorostyrene, p-chlorostyrene, divinylbenzene, glycidylacrylate,allylglycidylether, (2H-perfluoropropyl)-2-propenylether, linalooloxide,3-allyloxy-1,2-propanediol, 2-(allyloxy) ethanol, N-allylmorpholine,allylglycine, N-vinyl pyrrolidone, allyltrichlorosilane,acryltrimethylsilane, allyldimethyl(diisopropylamino)silane,7-octenyltrimethoxysilane and allyloxytrimethylsilane, allyloxytriphenylsilane. As the polar olefins, unsaturated carboxylic derivatives(especially, acid anhydrides, esters and amides), halogenated olefins orvinylesters are preferred.

[0552] In the polymerization, the way of charging the component (A) intoa polymerization reactor, usage of each component, the feeding processand the order of feeding can be chosen as desired, but for reference,some examples are given below.

[0553] (1) The component (A) and the component (B) are fed to thepolymerization reactor in an arbitrary order.

[0554] (2) A catalyst obtained by previously contacting the component(A) with the component (B) is fed to the polymerization reactor.

[0555] (3) A catalyst component obtained by previously contacting thecomponent (A) with the component (B), and the component (B) are fed tothe polymerization reactor in an arbitrary order. In this case, thesecomponents (B) may be the same or different.

[0556] (4) A catalyst component wherein the component (A) is supportedon the carrier (C), and the component (B) are fed to the polymerizationreactor in an arbitrary order.

[0557] (5) A catalyst wherein the component (A) and the component (B)are supported on the carrier (C) is fed to the polymerization reactor.

[0558] (6) A catalyst component wherein the component (A) and thecomponent (B) are supported on the carrier (C), and the component (B)are fed to the polymerization reactor in an arbitrary order. In thiscase, these components (B) may be the same or different.

[0559] (7) A catalyst component wherein the component (B) is supportedon the carrier (C), and the component (A) are fed to the polymerizationreactor in an arbitrary order.

[0560] (8) A catalyst component wherein the component (B) is supportedon the carrier (C), the component (A), and the component (B) are fed tothe polymerization reactor in an arbitrary order. In this case, thesecomponents (B) may be the same or different.

[0561] (9) A component wherein the component (A) is supported on thecarrier (C), and a component wherein the component (B) is supported onthe carrier (C) are fed to the polymerization reactor in an arbitraryorder.

[0562] (10) A component wherein the component (A) is supported on thecarrier (C), a component wherein the component (B) is supported on thecarrier (C), and the component (B) are fed to the polymerization reactorin an arbitrary order. In this case, these components (B) may be thesame or different.

[0563] (11) The component (A), the component (B) and the organiccompound component (D) are fed to the polymerization reactor in anarbitrary order.

[0564] (12) A component obtained by previously contacting the component(B) with the component (D), and the component (A) are fed to thepolymerization reactor in an arbitrary order.

[0565] (13) A component wherein the component (B) and the component (D)are supported on the carrier (C), and the component (A) are fed to thepolymerization reactor in an arbitrary order.

[0566] (14) A catalyst component obtained by previously contacting thecomponent (A) with the component (B), and the component (D) are fed tothe polymerization reactor in an arbitrary order.

[0567] (15) A catalyst component obtained by previously contacting thecomponent (A) with the component (B), the component (B) an d thecomponent (D) are fed to the polymerization reactor in an arbitraryorder. In this case, these components (B) may be the same or different.

[0568] (16) A catalyst component obtained by previously contacting thecomponent (A) with the component (B), and a component obtained bypreviously contacting the component (B) with the component (D) are fedto the polymerization reactor in an arbitrary order. In this case, thesecomponents (B) may be the same or different.

[0569] (17) A component wherein the component (A) is supported on thecarrier (C), the component (B) and the component (D) are fed to thepolymerization reactor in an arbitrary order.

[0570] (18) A component wherein the component (A) is supported on thecarrier (C), and a component obtained by previously contacting thecomponent (B) with the component (D) are fed to the polymerizationreactor in an arbitrary order.

[0571] (19) A catalyst component obtained by previously contacting thecomponent (A), the component (B) and the component (D) with one anotherin an arbitrary order is fed to the polymerization reactor.

[0572] (20) A catalyst component obtained by previously contacting thecomponent (A), the component (B) and the component (D) with one another,and the component (B) are fed to the polymerization reactor in anarbitrary order. In this case, these components (B) may be the same ordifferent.

[0573] (21) A catalyst wherein the component (A), the component (B) andthe component (D) are supported on the carrier (C) is fed to thepolymerization reactor.

[0574] (22) A catalyst component wherein the component (A), thecomponent (B) and the component (D) are supported on the carrier (C),and the component (B) are fed to the polymerization reactor in anarbitrary order. In this case, these components (B) may be the same ordifferent.

[0575] An olefin may be prepolymerized onto a solid catalyst componentwherein the component (A) and, if necessary, the component (B) aresupported on the carrier (C).

[0576] The polymerization can be carried out by any of liquid phasepolymerization such as solution polymerization or suspensionpolymerization, and gas phase polymerization.

[0577] Examples of an inert hydrocarbon media for use in the liquidphase polymerization include aliphatic hydrocarbons such as propane,butane, pentane, hexane, heptane, octane, decane, dodecane and kerosine;alicyclic hydrocarbons such as cyclopentane, cyclohexane andmethylcyclopentane; aromatic hydrocarbons such as benzene, toluene andxylene; halogenated hydrocarbons such as ethylene chloride,chlorobenzene and dichloromethane; and mixtures of these hydrocarbons. Anon-polar olefin or a polar olefin itself can be used as the solvent.

[0578] In the copolimerization of a non-polar olefin and a polar olefinusing the olefin polymerization catalyst as mentioned above, thecomponent (A) may be used in an amount of usually 10⁻¹² to 10⁻² mol,preferably 10⁻¹⁰ to 10⁻³ mol, based on 1 liter of the reaction volume.In the present invention, even if the component (A) is used in arelatively low concentration, an olefin can be polymerized with a highpolymerization activity.

[0579] The component (B-1) may be used in such an amount that the molarratio of the component (B-1) to the transition metal atom (M or M′) inthe component (A) ((B-1)/(M or M′)) becomes usually 0.01 to 100,000,preferably 0.05 to 50,000.

[0580] The component (B-2) may be used in such an amount that the molarratio of the aluminum atom in the component (B-2) to the transitionmetal atom (M or M′) in the component (A) ((B-2)/(M or M′)) becomesusually 10 to 500,000, preferably 20 to 100,000.

[0581] The component (B-3) may be used in such an amount that the molarratio of the component (B-3) to the transition metal atom (M or M′) inthe component (A) ((B-3)/(M or M′)) becomes usually 1 to 10, preferably1 to 5.

[0582] The component (D) may be used, when the component (B) is thecomponent (B-1), in such an amount that the molar ratio of (D)/(B-1)becomes usually 0.01 to 10, preferably 0.1 to 5; when the component (B)is the component (B-2), in such an amount that the molar ratio of(D)/(B-2) becomes usually 0.001 to 2, preferably 0.005 to 1; and whenthe component (B) is the component (B-3), in such an amount that themolar ratio of (D)/(B-3) becomes usually 0.01 to 10, preferably 0.1 to5.

[0583] There is no specific restriction on each amount of the non-polarolefin and the polar olefin used in the polymerization, and each properamount is determined according to the kind of olefin to be used andcopolymerization ratio of the copolymer to be obtained.

[0584] In using the polymerization catalyst as mentioned above, thepolymerization temperature may be in the range of usually −50 to 200°C., preferably 0 to 170° C. The polymerization pressure may be in therange of usually atmospheric pressure to 100 kg/cm², preferablyatmospheric pressure to 50 kg/cm². The polymerization reaction can alsobe carried out by any of batchwise, semi-continuous and continuousprocesses. Further the polymerization can be conducted in two or morestages under different reaction conditions.

[0585] The molecular weight of the resulting polar olefin copolymer canbe regulated by allowing hydrogen to be present in the polymerizationsystem or by changing the polymerization temperature. The molecularweight can also be regulated by changing the type of the component (B).

[0586] The polar olefin copolymer of the present invention, as comparedwith conventional olefin polymers, has excellent adhesion properties,coating properties, compatibility, hydrophilic properties, oilresistance and the like, so that it can be used in such applicationfields that those characteristics are used effectively.

[0587] Further, the polar olefin copolymer of the present invention canalso be used as modifiers by mixing with other polymers such aspolyethylene, polypropylene and the like.

[0588] According to the present invention, a polar olefin copolymer canbe produced by copolymerizing a non-polar olefin and a polar olefin witha high polymerization activity.

EXAMPLES

[0589] The present invention is further described with reference to thefollowing examples, but it should be construed that the invention is inno way limited to those examples.

[0590] The structures of the compounds obtained in the synthesisexamples were determined by 270 MHz ¹-H-NMR (Japan Electron OpticsLaboratory GSH-270 Model), FT-IR (SHIMADZU FTIR-8200D Model), FD-massspectrometry (Japan Electron Optics Laboratory SX-102A Model), metalcontent analysis (analysis by ICP method after dry ashing anddissolution in dilute nitric acid, device: SHIMADZU ICPS-8000 Model),and elemental analysis for carbon, hydrogen and nitrogen (Helaus CHNOModel).

[0591] The intrinsic viscosity (η) was measured in decalin at 135° C.

Synthesis Example 1

[0592] Synthesis of ligand precursor (L1)

[0593] To a 100-ml reactor thoroughly purged with nitrogen, 40 ml ofethanol, 0.71 g (7.62 mmol) of aniline and 1.35 g (7.58 mmol) of3-t-butylsalicylaldehyde were introduced and continuously stirred atroom temperature for 24 hours. The reaction solution was concentratedunder reduced pressure to remove the solvent, and the concentrate waspurified by a silica gel column to obtain 1.83 g (7.23 mmol, yield: 95%)of a compound (ligand precursor (L1)) represented by the followingformula (L1) as an orange oil.

[0594]¹H-NMR(CDCl₃): 1.47(s,9H), 6.88(dd,1H), 7.24-7.31(m,4H),7.38-7.46(m,3H), 8.64(s,1H), 13.95(s,1H)

[0595] IR(neat): 1575, 1590, 1610 cm⁻¹

[0596] FD-mass spectrometry: 253 (M⁺)

Synthesis Example 2

[0597] Synthesis of Ligand Precursor (L2)

[0598] Raction and purification were carried out in the same manner asin Synthesis Example 1 except that 0.95 g (7.58 mmol) of salicylaldehydewas used instead of the 3-t-butylsalicylaldehyde, to thereby obtain 1.39g (7.05 mmol, yield: 93%) of a compound (ligand precursor (L2))represented by the following formula (L2) as an orange solid-solution.

[0599] FD-mass spectrometry: 197 (M⁺)

Synthesis Example 3

[0600] Synthesis of Ligand Precursor (L3)

[0601] To a 100-ml reactor thoroughly purged with nitrogen, 150 ml ofethanol, 5.0 g (53 mmol) of aniline and 5.1 g (53 mmol) ofpyrrole-2-carboxyaldehyde were introduced and further 1 ml of a formicacid was added. Thereafter, the mixture was continuously stirred at roomtemperature for 24 hours. The reaction solution was concentrated underreduced pressure to remove the solvent, and the concentrate was purifiedby a silica gel column to obtain 6.0 g (34.9 mmol, yield: 66%) of acompound (ligand precursor (L3)) represented by the following formula(L3) as a white solid.

[0602]¹H-NMR(CDCl₃): 6.3(d,1H), 6.69(dd,1H), 6.89(d,1H), 7.1-7.5(m,4H),8.29(s,1H), 9.85(brs,1H)

[0603] FD-mass spectrometry: 170

Synthesis Example 4

[0604] Synthesis of Ligand Precursor (L4)

[0605] To a 200-ml reactor thoroughly purged with nitrogen, 5.0 g-of2,4-di-t-butylphenol and 50 ml of acetic acid were added. To themixture, 3.0 ml of concentrated nitric acid was rapidly dropwise addedunder cooling. After the dropwise addition was completed, the resultantmixture was stirred at the same temperature for 1 minute and poured into200 ml of water. The organic phase extracted with diethyl ether waswashed with water and concentrated. The concentrate was purified by acolumn chromatography to obtain 5.1 g (yield: 84%) of yellow crystals.

[0606] HNMR(CDCl₃, δ): 11.41(s,1H), 7.94(d,1H,2 Hz), 7.63(d,1H,2 Hz),1.43(s,9H), 1.29(s,9H)

[0607] Then, the total amount of the above-obtained compound, 50 mg of5% palladium carbon and 100 ml of ethanol were added to a 200-mlreactor, and the mixture was stirred for 48 hours under hydrogen of 1atmospheric pressure. The reaction solution was filtered through Celite,and then the solvent was distilled off to obtain 4.1 g (yield: 89%) ofwhite crystals.

[0608]¹HNMR(CDCl₃, δ): 6.92(d,1H,2 Hz), 6.82(d,1H,2 Hz), 5.70(s,1H),3.19(br1H), 141(s,9H), 1.28(s9H)

[0609] Subsequently, 2.83 g of the-above-obtained compound and 50 ml ofethanol were added to a 100-ml reactor thoroughly purged with nitrogen,and 1.63 g of benzaldehyde and 1.0 ml of acetic acid were further addedto the reactor. The mixture was stirred at room temperature for 24hours. The reaction solution was concentrated, and then the concentratewas purified by a column chromatography to obtain 3.2 g (yield: 80%) ofa compound (ligand precursor (L4)) represented by the following formula(L4) as yellow crystals.

[0610]¹HNMR(CDCl₃, δ): 8.70(s,1H), 7.96-7.92(m,2H), 7.73(s,1H),7.48-7.43(m,3H), 7.25(d,1H,2 Hz), 7.17(d,1H,2 Hz), 1.46(s,9H),1.35(s,9H)

Synthesis Example 5

[0611] Synthesis of Ligand Precursor (L5)

[0612] 1.40 g (12.8 mmol) of o-aminophenol and 50 ml of ethanol wereadded to a 100-ml reactor thoroughly purged with nitrogen, and 1.63 g(15.4 mmol) of benzaldehyde and 1.0 ml of acetic acid were further addedto the reactor. The mixture was stirred at room temperature for 24hours. The reaction solution was concentrated, and then the concentratewas separated and purified by a column chromatography to obtain 1.74 g(8.83 mmol, yield: 69%) of a compound (ligand precursor (L5))represented by the following formula (L5) as yellow crystals.

[0613]¹HNMR(CDCl ₃, δ): 8.71(s,1H), 7.95-7.88(m,2H)r 7.52-7.43(m,3H),7.32-7.16(m,3H) 7.04-6.86(m,2H)

[0614] FD-mass spectrometry: 197

Synthesis Example 6

[0615] Synthesis of Ligand Precursor (L6)

[0616] To a 300-ml reactor equipped with a Dean and Stark tube, 18.2 g(0.12 mol) of p-nitrobenzaldehyde, 50 ml of n-butanol, 500 mg ofp-toluenesulfonic acid monohydrate and 150 ml of toluene were added, andstirred under reflux for 2.5 hours. The reaction solution was cooleddown to room temperature and washed twice with 100 ml of an aqueoussolution of saturated sodium hydrogen carbonate and once with purewater. The resultant organic phase was dried with anhydrous magnesiumsulfate, followed by distilling off the solvent, and the resultantproduct was dried with a vacuum pump to obtain 30.9 g (yield: 92%) of acompound (a) represented by the following formula as a yellow oil.

[0617] To a 2-litter reactor thoroughly purged with nitorgen, 28.2 g(0.10 mol) of the above obtained compound (a) and 500 ml of dry THF wereintroduced, and they were cooled to −65° C. Subsequently, to thereactor, 330 ml (0.33 mol) of vinylmagnesiumbromide (1M, THF solution)was dropwise added with a dropping funnel over a period of 25 minutes,and they were stirred at −40° C. for 1 hour. The reaction solution waspoured into 1 liter of an aqueous solution of saturated ammoniumchloride and further 300 ml of diethylether was added, followed byrepeating extraction operation twice. The organic layer was concentratedand 200 ml of THF and 10 ml of 0.5 M hydrochloric acid aqueous solutionwere added to the concentrate, followed by stirring at room temperaturefor 20 minutes. Thereafter, 200 ml of an aqueous solution of saturatedsodium carbonate was added to confirm the mixture being PH>8. Then, anextraction operation with 100 ml of ethyl acetate was repeated twice,and the resultant product was purified by a column chromatography toobtain 10.6 g (yield: 73%) of a compound (b) represented by thefollowing formula as a light yellow solid.

[0618]¹HNMR(CDCl₃): 6.62-6.65(t,1H), 7.25-7.30(m,2H), 7.34-7.37(t,1H),7.65-7.68(d,1H), 7.93-7.97(d,1H), 10.13(s,1H)

[0619] FD-mass spectrometry: 145

[0620] Elemental analysis: Measured values (wt %) C 74.4; H 4.7; N 9.6Theoretical values (wt %) C 74.5; H 4.9; N 9.7

[0621] To a 100-ml reactor thoroughly purged with nitrogen, 1.20 g (8.27mmol) of the above-obtained compound (b), 40 ml of dewatered ethanol,0.77 g (8.27 mmol) of aniline and acetic acid (catalyst amount) wereadded, and they were stirred at room temperature for 3 hours. Thereaction solution was concentrated, and then the concentrate waspurified by a column chromatography to obtain 1.53 g (yield: 85%) of acompound (ligand precursor (L6)) represented by the following formula(L6) as a light yellow oil.

[0622]¹HNMR(CDCl₃): 6.50-6.60(t,1H), 7.10-7.40(m,8H), 8.63(s,1H),10.76(bs,1H)

[0623] FD-mass spectrometry: 220

Synthesis Example 7

[0624] Synthesis of Ligand Precursor (L7)

[0625] Reaction was carried out in the same manner as in SynthesisExample 1, except that 0.76 g (7.62 mmol) of cyclohexyl amine was usedinstead of aniline and 0.95 g (7.58 mmol) of salicyl aldehyde was usedinstead of 3-t-butylsalicylaldehyde. The solvent was distilled off toobtain 1.51 g (7.43 mmol, yield: 98%) of a compound (ligand precursor(L7)) represented by the following formula -(L7) as a yellow oil.

[0626] FD-mass spectrometry: 203

Synthesis Example 8

[0627] Synthesis of Ligand Precursor (L8)

[0628] Reaction was carried out in the same manner as in SynthesisExample 1, except that 1.15 g (7.58 mmol) of2-hydroxy-5-methoxybenzaldehyde was used instead of3-t-butylsalicylaldehyde. The solvent was distilled off to obtain 1.69 g(7.43 mmol, yield: 98%) of a compound (ligand precursor (L8))represented by the following formula (L8) as an orange oil.

[0629] FD-mass spectrometry: 227

Synthesis Example 9

[0630] Synthesis of Ligand Precursor (L9)

[0631] Reaction was carried out in the same manner as in SynthesisExample 1, except that 2.05 g (7.62 mmol) of n-octadecyl amine was usedinstead of aniline, 0.95 g (7.56 mmol) of salicyl aldehyde was usedinstead of 3-t-butylsalicylaldehyde, and as a solvent 120 ml of atoluene/ethanol mixed solvent (volume ratio: 5/1) was used instead ofethanol. The solvent was distilled off to obtain 2.75 g (7.35 mmol,yield: 97%) of a compound (ligand precursor (L9)) represented by thefollowing formula (L9) as a yellow oil.

[0632] FD-mass spectrometry: 373

Synthesis Example 10

[0633] Synthesis of Ligand Precursor (L10)

[0634] Reaction was carried out in the same manner as in SynthesisEx-ample 1, except that 0.34 g (3.81 mmol) of 1,4-tetramethylenediaminewas used instead of aniline and 0.95 g (7.58 mmol) of salicyl aldehydewas used instead of 3-t-butylsalicylaldehyde, and that the reaction wascarried out under reflux while dewatering through a Dean and Stark tube.After the solvent was distilled off, the resultant product wasrecrystallized from hot methanol (MeOH) to obtain 0.56 g (1.90 mmol,yield: 50%) of a compound (ligand precursor (L10)) represented by thefollowing formula (L10) as yellow crystals.

[0635] FD-mass spectrometry: 296

Synthesis Example 11

[0636] Synthesis of Ligand Precursor (L11)

[0637] Reaction was carried out in the same manner as in SynthesisExample 1, except that 0.44 g (3.81 mmol) of 1,6-hexamethylenediaminewas used instead of aniline and 0.95 g (7.58 mmol) of salicyl aldehydewas used instead of 3-t-butylsalicylaldehyde, and that the reaction wascarried out under reflux while dewatering through a Dean and Stark tube.After the solvent was distilled off, the resultant product wasrecrystallized from hot MeOH to obtain 1.13 g (3.49 mmol, yield: 92%) ofa compound (ligand precursor (L11)) represented by the following formula(L11) as yellow crystals.

[0638] FD-mass spectrometry: 324

Synthesis Example 12

[0639] Synthesis of ligand precursor (L12)

[0640] Reaction and purification were carried out in the same manner asin Synthesis Example 1, except that 0.82 g (7.62 mmol) of2-(aminomethyl)pyridine was used instead of aniline, to thereby obtain1.83 g (6.82 mmol, yield: 90%) of a compound (ligand precursor (L12))represented by the following formula (L12) as a yellow oil.

[0641] FD-mass spectrometry: 268

Synthesis Example 13

[0642] Synthesis of Ti-L1 Complex

[0643] To a 300-ml reactor thoroughly dried and purged with argon, 1.785g (7.05 mmol) of the ligand precursor (L1) and 100 ml of diethyl etherwere introduced, and they were cooled to −78° C. and stirred. To theresulting mixture, 4.78 ml of n-butyllithium (1.55 mmol/ml-n-hexanesolution, 7.40 mmol) was dropwise added over a period of 5 minutes, andthey were slowly heated to room temperature and continuously stirred atroom temperature for 4 hours to prepare a lithium salt solution. Thesolution was dropwise added slowly to a mixture solution of 7.05 ml (0.5mmol/ml-heptane solution, 3.53 mmol) of a titanium tetrachloridesolution and 40 ml of diethyl ether, said mixture having been cooled to−78° C. After the dropwise addition was completed, the reaction solutionwas slowly heated to room temperature with stirring. The reactionsolution was further stirred for another 8 hours at room temperature,and the solution was filtered through a glass filter to obtain a solid.The solid was dissolved in and washed with 50 ml of methylene chloride,and the insolubles were removed. The filtrate was concentrated underreduced pressure to precipitate a solid. The solid was dissolved in 10ml of methylene chloride and 70 ml of pentane was slowly added to thesolution with stirring. The mixture solution was allowed to stand atroom temperature to precipitate reddish brown crystals. The crystalswere filtered through a glass filter and washed with pentane. Theresultant crystals were vacuum dried to obtain 1.34 g (2.15 mmol, yield:61%) of a complex (1) represented by the following formula as reddishbrown crystals.

[0644]¹H-NMR(CDCl₃): 1.35(s,18 H), 6.82-7.43(m,16H) 8.07(s,2H)

[0645] IR(KBr): 1550, 1590, 1600 cm³¹ ¹

[0646] FD-mass spectrometry: 622 (M⁺)

[0647] Elemental analysis: Ti; 7.7% (7.7) C; 65.8% (65.5) H; 6.0% (5.8)N; 4.5% (4.5) The value in ( ) is calculated value.

Synthesis Example 14

[0648] Synthesis of Ti-L3 Complex

[0649] In a 100-ml reactor thoroughly dried and purged with argon, 16 mlof a diethyl ether solution of the ligand precursor (L3) (1.04 g, 6.08mmol) obtained in Synthesis Example 3 was introduced and cooled to −78°C. To the solution, 4.2 ml (6.08 mmol) of a 1.45 N n-BuLi/hexanesolution was dropwise added, and they were slowly heated to roomtemperature. The resultant solution was dropwise added slowly to amixture solution of 6.08 ml of a titanium tetrachloride solution (0.5mmol/ml-heptane solution, 3.04 mmol) and 16 ml of diethyl ether, saidmixture having been cooled to −78° C. After the dropwise addition wascompleted, the reaction solution was slowly heated to room temperaturewith stirring. The reaction solution was further stirred for another 8hours at room temperature, and the reaction solution was filteredthrough a glass filter. The filtrate was concentrated under reducedpressure to precipitate a solid. The solid was dissolved in 5 ml ofmethylene chloride, and 10 ml of hexane was slowly added to the solutionwith stirring. The mixture was allowed to stand at room temperature toprecipitate a blackish brown solid. The solid was filtered through aglass filter and washed with pentane. The resultant product was vacuumdried to obtain 1.10 g (2.40 mmol, yield: 79%) of a complex (2)represented by the following formula as a blackish brown solid.

[0650]¹H-NMR(CDCl₃): 6.0-7.9(m,16H), 7.80(s,2H)

[0651] FD-mass spectrometry: 456 (M⁺)

[0652] Elemental analysis Ti; 10.4% (10.5) The value in ( ) iscalculated value.

Synthesis Example 15

[0653] Synthesis of Ti-L4 Complex

[0654] 618 mg of the ligand precursor (L4) obtained in Synthesis Example4 was dissolved in 10 ml of toluene, and the resultant solution wasdropwise added to 10 ml of a toluene solution of titanium chloride (0.1mol/l) at room temperature with stirring. After the stirring was carriedout at the same temperature for 24 hours, the reaction mixture wasfiltered through a glass filter. To the resultant filtrate, 10 ml ofn-hexane was added, and the mixture was allowed to stand at −40° C. for5 hours to obtain a solid. The solid was separated by filtration toobtain 241 mg (yield: 33%) of a complex (3) represented by the followingformula as reddish brown crystals.

[0655] FD-MS:734 (M⁺), 307 (ligand fragment)

Synthesis Example 16

[0656] Synthesis of V-L2 Complex (1)

[0657] To a 300-ml reactor thoroughly dried and purged with argon, 0.99g (5.0 mmol) of the ligand precursor L2 and 100 ml of THF wereintroduced, and they were cooled to −78° C. and stirred. To theresulting mixture, 3.23 ml of n-butyllithium (1.55 mmol/ml-n-hexanesolution, 5.0 mmol) was dropwise added over a period of 5 minutes, andthey were slowly heated to room temperature and continuously stirred atroom temperature for 4 hours to prepare a lithium salt solution. Thesolution was dropwise added slowly to a mixture solution of 0.62 g (1.67mmol) of VCl₃.(THF)₃ and 40 ml of THF, said mixture having been cooledto −78° C. After the dropwise addition was completed, the reactionsolution was slowly heated to room temperature with stirring. Thereaction solution was further stirred for another 5 hours at roomtemperature, and THF was distilled off under reduced pressure to obtaina solid. The solid was dissolved in methylene chloride, and theinsolubles were removed by filtration. The filtrate was concentrated andpentane was slowly added to the concentrate with stirring to precipitatea reddish brown solid. The solid was separated by filtration through aglass filter and washed with pentane. The resultant solid was vacuumdried to obtain 0.44 g (0.69 mmol, yield: 41%) of a complex (4)represented by the following formula.

[0658] FD-MS: 639 (M⁺)

Synthesis Example 17

[0659] Synthesis of V-L2 Complex (2)

[0660] 3.30 g (13 mmol) of (VO) (SO₄).5H₂O was introduced and dissolvedin 100 ml of pure water, and the aqueous solution was dropwise added toa solution of 5.13 g (26 mmol) of the ligand precursor L2 and 100 ml of95% ethanol. To the mixture, further 50 ml of an aqueous solution of 4.6g (56 mmol) of sodium acetate was added and the reaction solution wasstirred for 20 minutes under reflux. The reaction solution was allowedto stand at room temperature for 2 hours to precipitate a dark greenpowder. The powder was separated by filtration through a glass filterand washed with water, ethanol and ether. The resultant powder wasvacuum dried to obtain 4.48 g (9.75 mmol, yield: 75%) of a complex (5)represented by the following formula.

[0661] FD-MS: 459 (M⁺)

Synthesis Example 18

[0662] Synthesis of Cr-L1 Complex

[0663] To a 300-ml reactor thoroughly dried and purged with argon, 1.785g (7.05 mmol) of the ligand precursor (L1) and 100 ml of THF wereintroduced, and they were cooled to −78° C. and stirred. To theresulting mixture, 4.78 ml of n-butyllithium (1.55 mmol/ml-n-hexanesolution, 7.40 mmol) was dropwise added over a period of 5 minutes, andthey were slowly heated to room temperature and stirred at roomtemperature for 4 hours to prepare a lithium salt solution. The solutionwas dropwise added slowly to a mixture solution of 0.558 g (3.53 mmol)of chromium trichloride and 40 ml of THF, said mixture having beencooled to −78° C. After the dropwise addition was completed, thereaction solution was slowly heated to room temperature with stirring.The reaction solution was further stirred for another 5 hours at roomtemperature, and the reaction solution was filtered through a glassfilter to obtain a solid. The solid was dissolved in and washed with 50ml of methylene chloride to remove insolubles. The filtrate was vacuumdried, and reprecipitated with ether/hexane to obtain a green powder.The powder was separated by filtration through a glass filter and washedwith hexane. The resultant powder was vacuum dried to obtain 1.04 g(1.76 mmol, yield: 50%) of a complex (6) represented by the followingformula.

[0664] FD-mass spectrometry: 592(M⁺)

[0665] Elemental analysis: Cr; 8.9% (8.8) C; 69.3% (69.0) H; 6.4% (6.1)N; 5.0% (4.7) The value in ( ) is calculated value.

Synthesis Example 19

[0666] Synthesis of Cu-L1 Complex

[0667] To a 100-ml egg-plant flask, 500 mg (1.97 mmol) of the ligandprecursor (L1) was introduced and dissolved in 30 ml of methanol, andthey were heated to 50° C. Separately, to another 50-ml egg-plant flask,200 mg (1.10 mmol) of copper acetate (II) was introduced and 15 ml ofmethanol was added to the flask and they were stirred with raising thetemperature to 50° C. This cupper acetate-methanol solution waspippetted into the methanol solution of the above ligand precursor (L1)with stirring to immediately precipitate a brown solid. The solidprecipitated was then cooled to room temperature, and was recovered byfiltration with a glass filter. The solid was washed with 20 ml ofmethanol twice and vacuum dried to obtain 510 mg (yield: 82%) of acomplex (7) represented by the-following formula as a luster brownsolid.

[0668] FD-mass spectrometry: 568 (M⁺)

Synthesis Example 20

[0669] Synthesis of V-L7 Complex

[0670] 1.10 g (4.86 mmol) of (VO) (SO₄).5H₂O was dissolved in 25 ml ofMeOH, and to the solution, a solution of 1.96 g (9.64 mmol) of theligand precursor L7 in 25 ml of MeOH was dropwise added at roomtemperature. To the mixture further 1 ml of pyridine was added, and thereaction solution was stirred for 2 hours under reflux. The resultantreaction solution was allowed to stand at room temperature for 2 hoursto precipitate a green powder. The powder was filtered off through aglass filter and washed with methanol. Then, the resultant powder wasvacuum dried to obtain 1.25 g (2.65 mmol, yield: 55%) of a complex (8)represented by the following formula as a green power.

[0671] FD-mass spectrometry: 471 (M⁺)

Synthesis Example 21

[0672] Synthesis of V-L8 Complex

[0673] Reaction and purification were carried out in the same manner asin Synthesis Example 20, except that 2.19 g (9.64 mmol) of the ligandprecursor (L8) was used instead of the ligand precursor (L7) and thereaction time was changed to 4 hours, to thereby obtain 0.39 g (0.74mmol, yield: 15%) of a complex (9) represented by the following formulaas a blue green power.

[0674] FD-mass spectrometry: 419 (M⁺)

Synthesis Example 22

[0675] Synthesis of V-L9 Complex

[0676] Reaction was carried out in the same manner as in SynthesisExample 20, except that 3.60 g (9.64 mmol) of the ligand precursor (L9)was used instead of the ligand precursor (L7) and the reaction solventwas changed to a toluene/methanol mixed solvent (volume ratio; 1/1)After the solvent was distilled off, the resultant product was extractedwith hexane, followed by evaporation to dryness. As a result, 2.39 g(2.94 mmol, yield: 61%) of a complex (10) represented by the followingformula was obtained as a light brown power.

[0677] FD-mass spectrometry: 811 (M⁺)

Synthesis Example 23

[0678] Synthesis of V-L10 Complex

[0679] Reaction and purification were carried out in the same manner asin Synthesis Example 20, except that 1.44 g (4.86 mmol) of the ligandprecursor (L10) was used instead of the ligand precursor (L7), thesolvent amount was changed to 100 ml and the pyridine amount was changedto 2 ml. As a result, 1.13 g (3.12 mmol, yield: 64%) of a complex (11)represented by the following formula was obtained as a yellowish greenpower.

[0680] FD-mass spectrometry: 361 (M⁺)

Synthesis Example 24

[0681] Synthesis of V-L11 Complex

[0682] Reaction and purification were carried out in the same manner asin Synthesis Example 20, except that 1.58 g (4.86 mmol) of the ligandprecursor (L11) was used instead of the ligand precursor (L7), thesolvent amount was changed to 100 ml and the pyridine amount was changedto 2 ml. As a result, 1.02 g (2.61 mmol, yield: 54%) of a complex (12)represented by the following formula was obtained as a yellowish greenpower.

[0683] FD-mass spectrometry: 389 (M⁺)

Synthesis Example 25

[0684] Synthesis of V-L12 Complex

[0685] To a 100-ml reactor thoroughly dried and purged with argon, 0.43g (1.61 mmol) of the ligand precursor (L12) and 15 ml of diethyletherwere introduced, and they were cooled to −78° C. and stirred. To theresulting mixture, 1.00 ml of n-butyllithium (1.59 mmol/ml-n-hexanesolution, 1.59 mmol) was dropwise added over a period of 10 minutes, andthey were slowly heated to room temperature and stirred at roomtemperature for 4 hours to prepare a lithium salt solution.

[0686] The solution was dropwise added slowly to a solution 0.59 g (1.57mmol) of VCl₃(thf)₃ in 15 ml of diethylether, having been cooled to −0°C. After the dropwise addition was completed, the reaction solution wasslowly heated to room temperature with stirring. The reaction solutionwas further stirred for another 3 hours at room temperature. After thestirring, the solvent was distilled off under reduced pressure. Then theremained yellowish brown solid was extracted with 30 ml of methylenechloride. The extract was filtered through a glass filter to concentrateto about 10 ml, and then 15 ml of hexane was added thereto. Theprecipitated solid was filtered off through a glass filter, washed withpentane and then vacuum dried to obtain 0.37 g (0.10 mmol, yield: 60%)of a complex (13) represented by the following formula (13) as ayellowish brown power.

[0687] FD-mass spectrometry: 388

Synthesis Example 26

[0688] Synthesis of Ti-L6 Complex

[0689] In a 50-ml Schlenk flask thoroughly degassed and purged withargon, 0.85 g (3.9 mmol) of the ligand precursor (L6) was dissolved in15 ml of diethylether, and the solution was cooled to −78° C. To themixture, 2.48 ml (3.9 nmol) of butyllithium (1.6 M hexane solution) wasslowly added with stirring, and the resultant mixture was graduallyheated to room temperature to prepare a lithium salt solution of theligand.

[0690] On the other hand, to another Schlenk flask thoroughly degassedand purged with argon, 3.86 ml (1.93 mmol) of titanium tetrachloride(0.5 M heptane solution) was introduced at −78° C., and further 6 ml ofdiethylether was added, and the mixture was slowly heated to roomtemperature with stirring. The solution was again cooled down to −78°C., and to the solution, the former prepared lithium salt solution ofthe ligand was dropwise added. The resultant mixture was stirredovernight at room temperature. After the solvent was distilled off witha vacuum pump, 30 ml of dichloromethane was added to filer offinsolubles. The filtrate was concentrated and subjected torecrystallization with a hexane-dichloromethane solvent to obtain 0.94 g(yield: 87%) of a complex (14) represented by the following formula as adark purple solid.

[0691] FD-mass spectrometry: 556

Synthesis Example 27

[0692] Synthesis of V-L4 Complex

[0693] In 50 ml of hexane, 2.50 g (8.1 mmol) of the ligand precursor(L4) was dissolved, and to the solution, 4.0 ml (6.4 mmol) of an-butyllithium hexane solution (1.6 M) was dropwise added at roomtemperature with stirring. After stirring for 1 hour at the sametemperature, the resulting yellow precipitate was separated byfiltration through a glass filter, washed with 15 ml of n-hexane andthen dried under vacuum to obtain 1.79 g of a lithium phenoxidederivative as a starting materiel compound. This compound was dissolvedin 50 ml of THF at room temperature, and the resulting solution wasdropwise added to 125 ml (2.86 mmol) of a vanadium trichloride THFsolution (0.023 M) having been cooled to −78° C., with stirring. Afterthe dropwise addition was completed, the reaction solution was heated toroom temperature and stirred for 12 hours. Then, the solvent was removedunder vacuum, and 50 ml of toluene was added at room temperature toprepare a solution. The solution was filtered through a glass filter toremove an inorganic salt contained in the solution. Then, the solutionwas concentrated to about 10 ml. To the solution, 80 ml of n-hexane wasadded, and they were stirred for one hour. Then, the resultingprecipitate was filtered off through a glass filter, washed with 20 mlof n-hexane and dried under vacuum to obtain 1.23 g of a complex (15)represented by the following structural formula (brown powder, yield:46%).

[0694] FD-MS (m/z): 703 (intensity 100%, M⁺) 309 (intensity 58%, ligandfragment)

Synthesis Example 28

[0695] Synthesis of V-L5 Complex

[0696] Reaction and purification were carried out in the same manner asin Synthesis Example 27, except that the ligand precursor (L5) was usedin place of the ligand precursor (L4). As a result, 1.23 g of a complex(16) represented by the following structural formula was obtained (brownpowder, yield: 48%).

[0697] FD-MS (m/z): 478 (intensity 100%, M⁺), 197 (intensity 52%, ligandfragment)

Example 1

[0698] Ethylene-norbornene Dicarboxylic Acid Anhydride Copolymer usingComplex (1)

[0699] To a 500-ml glass autoclave thoroughly purged with nitrogen, 250ml of toluene was introduced, and the liquid phase and the gas phasewere saturated with 0.5 mmcl of norbornene-2,3-dicarboxylic acidanhydride (hereinafter referred simply to as “NDCA”) and 100 l/hr ofethylene. Thereafter, 2.50 mmol (in terms of aluminum atom) ofmethylaluminoxane was added, and then 0.005 mmol of the complex (1)obtained in Synthesis Example 13 was added to initiate polymerization.The reaction was conducted at 25° C. for 10 minutes in an ethylene gasatmosphere at atmospheric pressure. Then, a small amount of isobutanolwas added to terminate the polymerization. After the polymerization wascompleted, the reaction product was introduced into a large amount ofmethanol to precipitate a total amount of a polymer. Then, hydrochloricacid was added, and the mixture was filtered through a glass filter. Theresulting polymer was sufficiently washed with methanol, and thenfurther vacuum dried at 80° C. for 10 hours to obtain 1.15 g of apolymer.

[0700] Measurements of IR and ¹³C-NMR of the polymer obtained werecarried out. As a result, the polymer proved to be an ethylene/NDCAcopolymer containing 0.02 mol % of NDCA.

[0701] Further, the coordination energy difference ΔE was calculatedunder the conditions that in the chemical formulas (2) and (3) describedabove, the ligand L was a ligand of the complex (1), the number a of theligands was 2, and the central metal M was Ti (IV) As a result, thecoordination energy difference ΔE was 20.3 kJ/mol.

Example 2

[0702] Ethylene-maleic Anhydride Copolymer using Complex (2)

[0703] Polymerization and post-treatment were carried out in the samemanner as in Example 1 except that the complex (2) obtained in SynthesisExample 14 was used instead of the complex (1) and 0.5 mmol of maleicanhydride was used instead of the NDCA, to thereby obtain 0.06 g of apolymer.

[0704] Measurements of IR and ¹³C-NMR of the polymer obtained werecarried out. As a result, the polymer proved to be an ethylene/maleicanhydride copolymer containing 0.01 mol % of maleic anhydride.

[0705] Further, the coordination energy difference ΔE was calculatedunder the conditions that in the chemical formulas (2) and (3) describedabove, the ligand L was a ligand of the complex (2), the number a of theligands was 2, and the central metal M was Ti (IV). As a result, thecoordination energy difference ΔE was 43.6 kJ/mol.

Example 3

[0706] Ethylene-norbornene Dicarboxylic Acid Anhydride Copolymer usingComplex (3)

[0707] To a 500-ml glass autoclave thoroughly purged with nitrogen, 250ml of toluene was introduced, and the liquid phase and the gas phasewere saturated with 100 l/hr of ethylene. Thereafter, 0.5 mmol of NDCAand 0.25 mmol of triisobutylalminum were added, and then 0.005 mmol ofthe complex (3) obtained in Synthesis Example 15 and 0.006 mmol oftriphenylcarbeniumtetrakis(pentafluorophenyl)borate were added toinitiate polymerization. The reaction was conducted at 75° C. for 30minutes in an ethylene gas atmosphere at atmospheric pressure. Then, asmall amount of isobutanol was added to terminate the polymerization.After the polymerization was completed, the reaction product wasintroduced into a large amount of methanol to precipitate a total amountof a polymer. Then, hydrochloric acid was added, and the mixture wasfiltered through a glass filter. The resulting polymer was sufficientlywashed with methanol, and then further vacuum dried at 80° C. for 10hours to obtain 0.13 g of a polymer.

[0708] Measurements of IR and ¹³C-NMR of the polymer obtained werecarried out. As a result, the polymer proved to be an ethylene/NDCAcopolymer containing 0.02 mol % of NDCA.

[0709] Further, the coordination energy difference ΔE was calculatedunder the conditions that in the chemical formulas (2) and (3) describedabove, the ligand L was a ligand of the complex (3), the number a of theligands was 2, and the central metal M was Ti (IV). As a result, thecoordination energy difference ΔE was 24.2 kJ/mol.

Example 4

[0710] Ethylene-norbornene Dicarboxylic Acid Anhydride Copolymer usingComplex (4)

[0711] To a 500-ml glass autoclave thoroughly purged with nitrogen, 250ml of toluene was introduced, and the liquid phase and the gas phasewere saturated with 100 l/hr of ethylene. Thereafter, 0.5 mmol of NDCAand 0.1 mmol of diethylaluminum chloride were added, and then 0.5 mmolof ethyltrichloroacetate and 0.005 mmol of the complex (4) obtained inSynthesis Example 16 were added to initiate polymerization. The reactionwas conducted at 25° C. for 10 minutes in an ethylene gas atmosphere atatmospheric pressure. Then, a small amount of isobutanol was added toterminate the polymerization. After the polymerization was completed,the reaction product was introduced into a large amount of methanol toprecipitate a total amount of a polymer. Then, hydrochloric acid wasadded, and the mixture was filtered through a glass filter. Theresulting polymer was sufficiently washed with methanol, and then vacuumdried at 80° C. for 10 hours to obtain 0.38 g of a polymer.

[0712] Measurements of IR and ¹³C-NMR of the polymer obtained werecarried out. As a result, the polymer proved to be an ethylene/NDCAcopolymer containing 0.03 mol % of NDCA.

[0713] Further, the coordination energy difference ΔE was calculatedunder the conditions that in the chemical formulas (2) and (3) describedin claim 1, the ligand L was a ligand of the complex (4), the number aof the ligands was 2, and the central metal M was V (III). As a result,the coordination energy difference ΔE was −26.9 kJ/mol.

Example 5

[0714] Ethylene-norbornene Dicarboxylic Acid Anhydride Copolymer usingComplex (5)

[0715] Polymerization and post-treatments were carried out in the samemanner as in Example 4 except that 0.5 mmol of the complex (5) obtainedin Synthesis Example 17 was used instead of the complex (4), to therebyobtain 0.24 g of a polymer.

[0716] Measurements of IR and ¹³C-NMR of the polymer obtained werecarried out. As a result, the polymer proved to be an ethylene/NDCAcopolymer containing 0.02 mol % of NDCA.

[0717] Further, the coordination energy difference ΔE was calculatedunder the conditions that in the chemical formulas (2) and (3) describedin claim 1, the ligand L was a ligand of the complex (5), the number aof the ligands was 2, and the central metal M was V (IV). As a result,the coordination energy difference ΔE was 9.1 kJ/mol.

Example 6

[0718] Ethylene-norbornene Dicarboxylic Acid Anhydride Copolymer usingComplex (6)

[0719] Polymerization and post-treatments were carried out in the samemanner as in Example 1 except that the complex (6) obtained in SynthesisExample 18 was used instead of the complex (1), to thereby obtain 0.05 gof a polymer.

[0720] Measurements of IR and ¹³C-NMR of the polymer obtained werecarried out. As a result, the polymer proved to be an ethylene/NDCAcopolymer containing 0.02 mol % of NDCA.

Example 7

[0721] Ethylene-methylmethacrylate Copolymer using Complex (7)

[0722] To a 500-ml glass polymerization reactor (equipped with astirring blade) thoroughly purged with nitrogen, 250 ml of toluene wasintroduced, and ethylene was blown into the toluene through a blowingtube for 10 minutes with slowly stirring. Thereafter, 3.39 ml (5 mmol)of a toluene solution of methylaluminoxane (Al concentration: 1.475 M),2.5 ml (0.025 mmol) of a toluene solution of the complex (7) (0.01 M)and 2 ml of methylmethacrylate were successively added and stirred at20° C. for 6 hours (600 rpm) with blowing ethylene at 50 l/hr. To thereaction solution, 25 ml of isobutanol and 5 ml of hydrochloric acidwere added to terminate the reaction. After stirring was carried out atroom temperature for 30 minutes, 1.5 liters of methanol was added to thereaction solution to obtain a slurry. The slurry was recovered byfiltration to obtain 958 mg of a polymer. The obtained polymer wasdetermined by IR, and as a result, it was found to be anethylene-methylmethacrylate copolymer containing carbonyl groups derivedfrom methylmethacrylate.

Example 8

[0723] Ethylene-maleic Anhydride Copolymer using Complex (1)

[0724] Polymerization and post-treatments were carried out in the samemanner as in Example 1 except that maleic anhydride was used instead ofthe NDCA, to thereby obtain 0.30 g of a polymer.

[0725] Measurements of IR and ¹³C-NMR of the polymer obtained werecarried out. As a result, the polymer proved to be an ethylene/maleicanhydride copolymer containing 0.02 mol % of maleic anhydride.

Example 9

[0726] Copolymerization of Ethylene and Norbornenedicarboxylic Acidusing Complex (14)

[0727] Polymerization and after-treatments were carried out in the samemanner as in Example 1, except that the complex (14) obtained inSynthesis Example 26 was used in place of the complex (1), the amount ofNDCA was changed to 2.0 mmol, and the polymerization time was changed to60 minutes. As a result, 0.03 g of a polymer was obtained. Then,measurements of IR and ¹³C-NMR of the polymer obtained were carried out.As a result, the polymer proved to be an ethylene/NDCA copolymercontaining NDCA in an amount of 0.02 mol based on 100 mol of theethylene unit.

Comparative Example 1

[0728] Polymerization was carried out in the same manner as in Example1, except that dicyclopentadienyltitanium dichloride (CP₂TiCl₂) was usedin place of the complex (1). As a result, any polymer was not obtained.

[0729] Further, the coordination energy difference ΔE was calculatedunder the conditions that in the chemical formulas (2) and (3) describedin claim 1, the ligand L was a cyclopentadienyl group, the number a ofthe ligands was 2, and the central metal M was Ti (IV). As a result, thecoordination energy difference ΔE was 93.1 kJ/mol.

Comparative Example 2

[0730] Polymerization was carried out in the same manner as in Example5, except that dicyclopentadienyltitanium dichloride was used in placeof the complex (5). As a result, any polymer was not obtained.

Examples 10-17

[0731] Copolymerization of Ethylene and Polar Olefin using Complexes (5)and (15)

[0732] In a 500 ml glass autoclave thoroughly purged with nitrogen, 250ml of hexane was placed, and ethylene was fed at a feed rate shown inTable 1 to saturate the liquid phase and the gas phase with ethylene.Thereafter, a polar olefin shown in Table 1, diethylaluminum chloride orethylaluminum dichloride as a co-catalyst and then the complex (5) orthe complex (15) as a catalyst were added in amounts shown in Table 1 toinitiate polymerization. With blowing ethylene into the autoclave,polymerization was conducted at 25° C. for a period of time shown inTable 1, and then a small amount of isobutanol was added to terminatethe polymerization. After the polymerization was completed, the reactionproduct was introduced into a large amount of methanol acidified withhydrochloric acid, to precipitate the whole polymer, followed byfiltration through a glass filter. The polymer was sufficiently washedwith methanol and then vacuum dried at 80° C. for 10 hours.

[0733] The yield of the polymer, (η) and a polar olefin contentdetermined by ¹³C-NMR are set forth in Table 1. In all polymersobtained, a polar olefin was contained, and the polymers obtained wereethylene/polar olefin copolymers. TABLE 1 Example10 Example11 Example12Example13 polymerization conditions polar olefin type

amount (mmol) 6 6 6 6 caalyst type complex(5) complex(5) complex(15)complex(5) amount (mmol) 0.04 0.04 0.04 0.04 co-catalyst type DCL DCLDCL DCL amount (mmol) 8 8 8 8 ethylene flow rate (L/hr) 100 100 100 100polymerization time (min) 5 30 30 30 polymerization polymer yield (g)1.47 0.31 0.35 0.38 results [η] (dl/g) 7.42 1.09 1.15 1.18 polar olefin0.03 0.26 0.54 0.30 content (mol %) Example14 Example15 Example16Example17 polymerization conditions polar olefin type

amount (mmol) 6 6 40 40 caalyst type complex(5) complex(15) complex(5)complex(15) amount (mmol) 0.04 0.04 0.025 0.025 co-catalyst type DEACDEAC DEAC DEAC amount (mmol) 8 8 50 50 ethylene flow rate (L/hr) 100 1002 2 polymerization time (min) 5 5 60 90 polymerization polymer yield (g)2.74 3.14 3.76 3.76 results [η] (dl/g) polar olefin 5.30 5.12 1.02 1.50content (mol %) 0.80 0.40 6.7 6.3

Examples 18-21

[0734] Copolymerization of Ethylene and Methyl Acrylate using Complexes(8), (9), (10) and (13)

[0735] Polymerization and after-treatments were carried out in the samemanner as in Example 10, except that the complex used as a catalyst wasreplaced with a complex shown in Table 2.

[0736] The yield of the polymer, (η) and a methyl acrylate contentdetermined by 13C-NMR are set forth in Table 2, in which the results ofExample 10 wherein the polymerization was conducted under the sameconditions are also set forth. In all polymers obtained, methyl acrylatewas contained, and the polymers obtained were ethylene/methyl acrylatecopolymers.

Examples 22-23

[0737] Copolymerization of Ethylene and Methyl Acrylate using Complexes(11) and (12)

[0738] Polymerization and after-treatments were carried out in the samemanner as in Example 10, except that 4 mmol of ethyl trichloroacetatewas added prior to the addition of the catalyst at the beginning of thepolymerization and the complex used as a catalyst was replaced with acomplex shown in Table 2.

[0739] The yield of the polymer, (η) and a methyl acrylate contentdetermined by ¹³C-NMR are set forth in Table 2, in which the results ofExample 10 are also set forth. In all polymers obtained, methyl acrylatewas contained, and the polymers obtained were ethylene/methyl acrylatecopolymers. TABLE 2 Example 10 Example 18 Example 19 Example 20 Example21 Example 22 Example 23 catalyst Complex (5) Complex (8) Complex (9)Complex (10) Complex (13) Complex (11) Complex (12) polymer yield (g)1.47 0.07 2.15 0.5  1.48 1.77 0.89 [η] (dl/g) 7.42 7.56 7.38 7.58 8.247.15 7.26 methyl acrylate 0.03 0.05 0.02 0.08 0.02 0.07 0.05 content(mol %)

Examples 24-28

[0740] Copolymerization of Ethylene, Propylene and Methyl Acrylate usingComplexes (5) and (15)

[0741] In a 500 ml glass autoclave thoroughly purged with nitrogen, 250ml of hexane was placed, and an ethylene/propylene mixed gas was fed ata feed rate shown in Table 3 to saturate the liquid phase and the gasphase with the mixed gas Thereafter, 6 mmol of methyl acrylate, 8 mmolof diethylaluminum chloride or ethylaluminum dichloride as a co-catalystand then 0.04 mmol of the complex (5) or the complex (15) as a catalystwere added to initiate polymerization. With blowing theethylene/propylene mixed gas into the autoclave, polymerization wasconducted at 25° C. for a period of time shown in Table 3, and then asmall amount of isobutanol was added to terminate the polymerization.After the polymerization was completed, the reaction product wasintroduced into a large amount of methanol acidified with hydrochloricacid, to precipitate the whole polymer, followed by filtration through aglass filter. Then, operations of sufficiently washing the polymer withmethanol, dissolving the polymer in hot toluene and introducing theresulting solution into a large amount of methanol to precipitate apolymer were repeated twice to purify the polymer. Thereafter, thepolymer was vacuum dried at 130° C. for 10 hours.

[0742] The yield of the polymer, (η), and a propylene content and amethyl acrylate content determined by ¹³C-NMR are set forth in Table 3.In all polymers obtained, methyl acrylate was contained, and thepolymers obtained were ethylene/propylene/methyl acrylate copolymers.

[0743] The monomer-monomer sequence distribution of the copolymerobtained in Example 26 was measured by ¹³C-NMR, and as a result, thecopolymer had an ethylene-ethylene sequence proportion of 65.4 mol %, anethylene-propylene sequence proportion of 32.0 mol %, an ethylene-methylacrylate sequence proportion of 0 .2 mol %, a propylene-propylenesequence proportion of 1.6 mol %, a propylene-methyl acrylate sequenceproportion of 0.7 mol % and a methyl acrylate-methyl acrylate sequenceproportion of 0.1 mol %. TABLE 3 Example 24 Example 25 Example 26Example 27 Example 28 catalyst Complex (5) Complex (5) Complex (15)Complex (16) Complex (15) co-catalyst (*) DEAC DCL DCL DCL DCLethylene/propylene flow rate (L/hr) 60/40 60/40 60/40 60/40 60/80polymerization time (min) 5 5 10 10 10 polymer yield (g) 0.14 0.71 4.571.82 2.52 [η] (dl/g) 1.47 4.67 3.75 4.01 3.54 propylene content (mol %)9.0 13.7 19.0 1 7.6 38.6 methyl acrylate content (mol %) 0.2 0.5 0.6 0.31.0

Example 29

[0744] Copolymerization of Ethylene, Propylene and Methyl Acrylate usingComplex (5) (in the Presence of Ethyl Trichloroacetate)

[0745] Polymerization and after-treatments were carried out in the samemanner as in Example 26, except that 4 mmol of ethyl trichloroacetatewas added after the addition of ethylaluminum dichloride. As a result,2.76 g of a polymer was obtained. Then, measurement of ¹³C-NMR of thepolymer obtained was carried out, and as a result, the polymer proved tobe an ethylene/propylene/methyl acrylate copolymer containing 1.6 mol %of methyl acrylate. The propylene content was 11.6 mol %, and (η) was1.75 dl/g.

Example 30

[0746] Copolymerization of Ethylene, Propylene and Methyl Acrylate usingComplex (15) (in the Presence of Hydrogen)

[0747] Polymerization and after-treatments were carried out in the samemanner as in Example 26, except that a mixed gas obtained by furtheradding 20 l/hr of hydrogen to the ethylene/propylene mixed gas was used.As a result, 2.37 g of a polymer was obtained. Then, measurement of¹³C-NMR of the polymer obtained was carried out, and as a result, thepolymer proved to be an ethylene/propylene/methyl acrylate copolymercontaining 0.6 mol % of methyl acrylate. The propylene content was 19.4mol %, and (η) was 2.31 dl/g.

Example 31

[0748] Measurement of Heat-sealing Strength of Ethylene/Propylene/MethylAcrylate Copolymer to Aluminum

[0749] A sheet (thickness: 100 μm) of the copolymer obtained in Example30 was prepared, and the sheet was cut into a strip. The strip wasinterposed between aluminum foils (thickness: 50 pm) having the samewidth as that of the strip, and they were heat-sealed at 200° C. for 5seconds by a heat sealer. From the sealed portion, a strip having awidth of 15 mm was cut out, and the peel strength was measured under theconditions of a peel angle of 180° and a peel rate of 200 m/min. As aresult, the peel strength was 0.90 kg/15 min.

[0750] On the other hand, the peel strength of an ethylene/propylenecopolymer (propylene content: 18.4 mol %, (η): 2.29 dl/g) containing nomethyl acrylate was measured in the same manner as described above. As aresult, the peel strength was 0.08 kg/15 min.

[0751] It was proved that the ethylene/propylene/methyl acrylatecopolymer obtained in Example 30 had a higher peel strength and higheradhesion properties to aluminum.

Example 32

[0752] Measurement of Contact Angle of Ethylene/Propylene/MethylAcrylate Copolymer

[0753] A film of the copolymer obtained in Example 30 was prepared usinga hot toluene solution of the copolymer. The film was subjected to adroplet method to measure a forward contact angle and a backward contactangle of the copolymer against water. As a result, the forward contactangle was 60°, and the backward contact angle was 93°.

[0754] On the other hand, the forward contact angle and the backwardcontact angle of an ethylene/propylene copolymer (propylene content:18.4 mol %, (η): 2.29 dl/g) containing no methyl acrylate was measuredin the same manner as described above. As a result, the forward contactangle was 88°, and the backward contact angle was 105°.

[0755] It was proved that the ethylene/propylene/methyl acrylatecopolymer obtained in Example 30 had smaller contact angles and higherwetting properties to water.

What is claimed is:
 1. A process for preparing a polar olefin copolymercomprising: copolymerizing a non-polar olefin and a polar olefin in thepresence of a catalyst comprising (A0) a compound of a transition metalselected from Groups 3 to 11 of the periodic table, which is representedby the following formula (1): L_(m)MX_(n)  (1) wherein M is a transitionmetal atom selected from Groups 3 to 11 of the periodic table, m is aninteger of 1 to 6, n is a number satisfying a valence of M, L is aligand coordinated to M and each ligand L has a feature that when thevalue obtained by subtracting the total sum of the whole energy, asdetermined by a density functional method, of the compounds on theleft-hand member from the whole energy, as determined by a densityfunctional method, of the compound on the right-hand member in thefollowing chemical formula (2) and the value obtained by the samesubtraction in the following chemical formula (3) are defined ascoordination energy E₁ of ethylene and coordination energy E₂ of methylacrylate, respectively, the difference ΔE (ΔE=E₁-E₂) between thecoordination energy E₁ of ethylene and the coordination energy E₂ ofmethyl acrylate is 50 kJ/mol or less,

wherein M is the same transition metal atom selected from Groups 3 to 11of the periodic table as M in the formula (1), a is an integer of 1 to3, b is an electric charge of the compound in the blankets [ ] and is 0or 1, and Me is a methyl group, and X is a hydrogen atom, a halogenatom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group, a boron-containinggroup, an aluminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residual group,silicon-containing group, a germanium-containing group and atin-containing group, and when n is 2 or greater, plural atoms or groupsindicated by X may be the same or different, and plural groups indicatedby X may be bonded to each other to form a ring.
 2. A process forpreparing a polar olefin copolymer comprising copolymerizing a non-polarolefin and a polar olefin in the presence of a catalyst comprising (A0)a compound of a transition metal selected from Groups 3 to 11 of theperiodic table, which is represented by the formula (1) as defined inclaim 1, and (B) at least one compound selected from the groupconsisting of (B-1) an organometallic compound, (B-2) an organoaluminumoxy-compound, and (B-3) a compound which reacts with a transition metalcompound (A0) to form an ion pair.
 3. The process for preparing a polarolefin copolymer as claimed in claim 1 or 2, wherein the transitionmetal compound represented by the general formula (1) is a compound of atransition metal selected from Groups 4, 5, 6 and 11 of the periodictable.
 4. A process for producing a polar olefin copolymer comprisingcopolymerizing a non-polar olefin and a polar olefin in the presence ofa catalyst comprising: (A1) a reaction product of (C) a compound of atransition metal selected from Groups 4, 5, 6 and 11 of the periodictable which is represented by the following formula (c): M′X_(k)  (c)wherein M′ is a transition metal atom selected from Groups 4, 5, 6 and11 of the periodic table, k is a number satisfying a valence of M′, andX is a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbongroup, an oxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residual group, asilicon-containing group, a germanium-containing group or atin-containing group, and when k is 2 or greater, plural atoms or groupsindicated by X may be the same or different, and plural groups indicatedby X may be bonded to each other to form a ring, and (A-i) a compoundrepresented by the following formula (I):

wherein A is an oxygen atom, a sulfur atom or a selenium atom, or anitrogen atom having a substituent R⁶, and R¹ to R⁶ may be the same ordifferent, they are each a hydrogen atom, a halogen atom, a hydrocarbongroup, an oxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, a heterocycliccompound residual group, a silicon-containing group, agermanium-containing group or a tin-containing group, two or more ofthem may be bonded to each other to form a ring; and (B) at least onecompound selected from the group consisting of: (B-1) an organometalliccompound, (B-2) an organoaluminum oxy-compound, and (B-3) a compoundwhich reacts with the reaction product (A1) to form an ion pair.
 5. Aprocess for producing a polar olefin copolymer comprising copolymerizinga non-polar olefin and a polar olefin in the presence of a catalystcomprising: (A2) a reaction product of (C) a compound of a transitionmetal selected from Groups 4, 5, 6 and 11 of the periodic table which isrepresented by the following formula (c): M′X_(k)  (c) wherein M′ is atransition metal atom selected from Groups 4, 5, 6 and 11 of theperiodic table, k is a number satisfying a valence of M′, and X is ahydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group, anoxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residual group, asilicon-containing group, a germanium-containing group or atin-containing group, and when k is 2 or greater, plural atoms or groupsindicated by X may be the same or different, and plural groups indicatedby X may be bonded to each other to form a ring, and (A-ii) a compoundrepresented by the following formula (II):

wherein D is a nitrogen atom or a phosphorus atom, Q is a nitrogen atomor a phosphorus atom, or a carbon atom substituted with a substituentR¹³, S is a nitrogen atom or a phosphorus atom, or a carbon atomsubstituted with a substituent R¹⁴, T is a nitrogen atom or a phosphorusatom, or a carbon atom substituted with a substituent R¹⁵, R¹¹ to R¹⁶may be the same or different, they are each a hydrogen atom, a halogenatom, a hydrocarbon group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group, a boron-containinggroup, an aluminum-containing group, a phosphorus-containing group, aheterocyclic compound residual group, a silicon-containing group, agermanium-containing group or a tin-containing group, two or more ofthem may be bonded to each other to form a ring; and (B) at least onecompound selected from the group consisting of: (B-1) an organometalliccompound, (B-2) an organoaluminum oxy-compound, and (B-3) a compoundwhich reacts with the reaction product (A2) to form an ion pair.
 6. Aprocess for producing a polar olefin copolymer comprising copolymerizinga non-polar olefin and a polar olefin in the presence of a catalystcomprising: (A3) a reaction product of (C′) a compound of a transitionmetal selected from Groups 3 to 11 of the periodic table, which isrepresented by the following formula (c′): MX_(k)  (c′) wherein M is atransition metal atom selected from Groups 3 to 11 of the periodictable, k is a number satisfying a valence of M, and X is a hydrogenatom, a halogen atom, an oxygen atom, a hydrocarbon group, anoxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residual group, asilicon-containing group, a germanium-containing group or atin-contalning group, and when k is 2 or greater, plural atoms or groupsindicated by X may be the same or different, and plural groups indicatedby X may be bonded to each other to form a ring, and (A-iii) a compoundrepresented by the following formula (III):

wherein A is an oxygen atom, a sulfur atom or a selenium atom, or anitrogen atom having a substituent R²⁶, and R²¹ to R²⁸ may be the sameor different, they are each a hydrogen atom, a halogen atom, ahydrocarbon group, an oxygen-containing group, a sulfur-containinggroup, a nitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, a heterocycliccompound residual group, a silicon-containing group, agermanium-containing group or a tin-containing group, two or more ofthem may be bonded to each other to form a ring.
 7. A process forproducing a polar olefin copolymer comprising copolymerizing a non-polarolefin and a polar olefin in the presence of a catalyst comprising: (A3)a reaction product of (C′) a compound of a transition metal selectedfrom Groups 3 to 11 of the periodic table, which is represented by thefollowing formula (c′): MX_(k)  (c′) wherein M is a transition metalatom selected from Groups 3 to 11 of the periodic table, k is a numbersatisfying a valence of M, and X is a hydrogen atom, a halogen atom, anoxygen atom, a hydrocarbon group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group, a boron-containinggroup, an aluminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residual group, asilicon-containing group, a germanium-containing group or atin-containing group, and when k is 2 or greater, plural atoms or groupsindicated by X may be the same or different, and plural groups indicatedby X may be bonded to each other to form a ring, and (A-iii) a compoundrepresented by the following formula (III):

wherein A is an oxygen atom, a sulfur atom or a selenium atom, or anitrogen atom having a substituent R²⁶, and R²¹ to R²⁸ may be the sameor different, they are each a hydrogen atom, a halogen atom, ahydrocarbon group, an oxygen-containing group, a sulfur-containinggroup, a nitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, a heterocycliccompound residual group, a silicon-containing group, agermanium-containing group or a tin-containing group, two or more ofthem may be bonded to each other to form a ring; and (B) at least onecompound selected from the group consisting of: (B-1) an organometalliccompound, (B-2) an organoaluminum oxy-compound, and (B-3) a compoundwhich reacts with the transition metal compound (A3) to form an ionpair.
 8. The process for producing a polar olefin copolymer as claimedin claim 6 or 7, wherein the compound of a transition metal representedby the formula (c′) is a compound of a transition metal selected fromGroups 4, 5, 6 and 11 of the periodic table.
 9. A process for producinga polar olefin copolymer comprising copolymerizing a non-polar olefinand a polar olefin in the presence of a catalyst comprising: (A4) acompound of a transition metal selected from Groups 4, 5, 6 and 11 ofthe periodic table, which is represented by the following formula (IV):

wherein M′ is a transition metal atom selected from Groups 4, 5, 6 and11 of the periodic table, m is an integer of 1 to 6, A is an oxygenatom, a sulfur atom or a selenium atom, or a nitrogen atom having asubstituent R⁶, R¹ to R⁴ and R⁶ may be the same or different, they areeach a hydrogen atom, a halogen atom, a hydrocarbon group, aheterocyclic compound residual group, an oxygen-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a sulfur-containing group, aphosphorus-containing group, a silicon-containing group, agermanium-containing group or a tin-containing group, two or more ofthem may be bonded to each other to form a ring, and when m is 2 orgreater, one group of R¹ to R⁴ and R⁶ contained in one ligand and onegroup of R¹ to R⁴ and R⁶ contained in other ligands may be bonded, andR¹s, R²s, R³s, R⁴s or R⁶s may be the same or different, n is a numbersatisfying a valence of M′, and X is a hydrogen atom, a halogen atom, anoxygen atom, a hydrocarbon group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group, a boron-containinggroup, an aluminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residual group, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or greater, plural atoms or groupsindicated by X may be the same or different, and plural groups indicatedby X may be bonded to each other to form a ring; and (B) at least onecompound selected from the group consisting of: (B-1) an organometalliccompound, (B-2) an organoaluminum oxy-compound, and (B-3) a compoundwhich reacts with the transition metal compound (A4) to form an ionpair.
 10. A process for producing a polar olefin copolymer comprisingcopolymerizing a non-polar olefin and a polar olefin in the presence ofa catalyst comprising: (A5) a compound of a transition metal selectedfrom Groups 4, 5, 6 and 11 of the periodic table which is represented bythe following formula (V)

wherein M′ is a transition metal atom selected from Groups 4, 5, 6 and11 of the periodic table, m is an integer of 1 to 6, D is a nitrogenatom or a phosphorus atom, Q is a nitrogen atom or a phosphorus atom, ora carbon atom substituted with a substituent R¹³, S is a nitrogen atomor a phosphorus atom, or a carbon atom substituted with a substituentR¹⁴, T is a nitrogen atom or a phosphorus atom, or a carbon atomsubstituted with a substituent R¹⁵, R¹¹ to R¹⁵ may be the same ordifferent, they are each a hydrogen atom, a halogen atom, a hydrocarbongroup, an oxygen-containing group, a sulfur-containing group, anitrogen-containing group, a boron-containing group, analuminum-containing group, a phosphorus-containing group, a heterocycliccompound residual group, a silicon-containing group, agermanium-containing group or a tin-containing group, two or more ofthem may be bonded to each other to form a ring, and when m is 2 orgreater, one group of R¹¹ to R¹⁵ contained in one ligand and one groupof R¹¹ to R¹⁵ contained in other ligands may be bonded, and R¹¹s, R¹²s,R¹³s, R¹⁴s or R¹⁵s may be the same or different, n is a numbersatisfying a valence of M′, and X is a hydrogen atom, a halogen atom, anoxygen atom, a hydrocarbon group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group, a boron-containinggroup, an aluminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residual group, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or greater, plural atoms or groupsindicated by X may be the same or different, and plural groups indicatedby X may be bonded to each other to form a ring; and (B) at least onecompound selected from the group consisting of: (B-1) an organometalliccompound, (B-2) an organoaluminum oxy-compound, and (B-3) a compoundwhich reacts with the transition metal compound (A5) to form an ionpair.
 11. A process for producing a polar olefin copolymer comprisingcopolymerizing a non-polar olefin and a polar olefin in the presence ofa catalyst comprising: (A6) a compound of a transition metal selectedfrom Groups 3 to 11 of the periodic table, which is represented by thefollowing formula (VI):

wherein M is a transition metal atom selected from Groups 3 to 11 of theperiodic table, m is an integer of 1 to 6, A is an oxygen atom, a sulfuratom or a selenium atom, or a nitrogen atom having a substituent R²⁶,R²¹ to R²⁷ may be the same or different, they are each a hydrogen atom,a halogen atom, a hydrocarbon group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group, a boron-containinggroup, an aluminum-containing group, a phosphorus-containing group, aheterocyclic compound residual group, a silicon-containing group, agermanium-containing group or a tin-containing group, two or more ofthem may be bonded to each other to form a ring, and when m is 2 orgreater, one group of R²¹ to R²⁷ contained in one ligand and one groupof R²¹ to R²⁷ contained in other ligands may be bonded, and R²¹s, R²²s,R²³s, R²⁴s, R²⁵s, R²⁶s or R²⁷s may be the same or different, n is anumber satisfying a valence of M, and X is a hydrogen atom, a halogenatom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group, a boron-containinggroup, an aluminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residual group, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or greater, plural atoms or groupsindicated by X may be the same or different, and plural groups indicatedby X may be bonded to each other to form a ring.
 12. A process forproducing a polar olefin copolymer comprising copolymerizing a non-polarolefin and a polar olefin in the presence of a catalyst comprising: (A6)a compound of a transition metal selected from Groups 3 to 11 of theperiodic table, which is represented by the following formula (VI):

wherein M is a transition metal atom selected from Groups 3 to 11 of theperiodic table, m is an integer of 1 to 6, A is an oxygen atom, a sulfuratom or a selenium atom, or a nitrogen atom having a substituent R²⁶,R²¹ to R²⁷ may be the same or different, they are each a hydrogen atom,a halogen atom, a hydrocarbon group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group, a boron-containinggroup, an aluminum-containing group, a phosphorus-containing group, aheterocyclic compound residual group, a silicon-containing group, agermanium-containing group or a tin-containing group, two or more ofthem may be bonded to each other to form a ring, and when m is 2 orgreater, one group of R²¹ to R²⁷ contained in one ligand and one groupof R²¹ to R²⁷ contained in other ligands may be bonded, and R²¹S, R²²s,R²³S, R²⁴S, R²⁵s, R²⁶s or R²⁷s may be the same or different, n is anumber satisfying a valence of M, and X is a hydrogen atom, a halogenatom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, asulfur-containing group, a nitrogen-containing group, a boron-containinggroup, an aluminum-containing group, a phosphorus-containing group, ahalogen-containing group, a heterocyclic compound residual group, asilicon-containing group, a germanium-containing group or atin-containing group, and when n is 2 or greater, plural atoms or groupsindicated by X may be the same or different, and plural groups indicatedby X may be bonded to each other to form a ring; and (B) at least onecompound selected from the group consisting of: (B-1) an organometalliccompound, (B-2) an organoaluminum oxy-compound, and (B-3) a compoundwhich reacts with the transition metal compound (A6) to form an ionpair.
 13. The process for producing a polar olefin copolymer as claimedin claim 11 or 12, wherein the compound of a transition metalrepresented by the formula (VI) is a compound of a transition metalselected from Groups 4, 5, 6 and 11 of the periodic table.
 14. A polarolefin copolymer obtained by the process according to any one of claims1 to 13.